DE2540624B2 - SPICING AND FLAVORING MATERIAL AND METHOD FOR PRODUCING THEREOF - Google Patents

Description

(a) / J-Jonon intimately in the presence of a buffer mixture! is made with a peralkanoic acid of the formula

R C

O OH

alone oiler

(ii) from a major proportion of 2,6,6-trimethyl-cyclohexyl-1-ylacelaldehyde and one, two or three of the compounds: 2,6,6-trimethyl-crotonyl-L.Vcyclohexadiene the formula

or one of the phenyl ('(, - ketones of the formula

wherein the dashed line is a carbon-carbon finf; bond or a carbon-carbon double bond means,

and as an auxiliary at least one compound from at most one of groups 1, 11 or III, namely

Group 1 for food:

p-hydroxybenzyl acetone, maltol, benzyl acetate,
Methyl cinnamate, geraniol,
Ethyl methylphenyl glycidate, vanillin,
Methyl anthranilate, (x-ionon, y-undecalactone,
Ethyl pelargonate, isoamyl acetate, acetaldehyde,
Dimethyl sulfide, isobutyl acetate, acetic acid,
Ethyl butyrate, diacetyl, anethole,
cis-3-hexenol-1, naphthyl ethyl ether,
Ethyl acetate, isoamyl butyrate,
2-methyl-2-pentenoic acid,
2 (4-hydroxy-4-methyl-pentylnorbornadiene,
4-allyl-1,2,6-trimethoxybenzene and
4-propenyl-1,2,6-trimethoxyben / ol;

Group Il for perfumeries:

Natural or synthetic perfume oils, alcohols, aldehydes, ketones, F.ster or lactones;

G nippe 111 for tobacco products:

Ethyl butyrate, ethyl valerate or maltol.

2. Process for the production of the main seasoning Serving 2,6, b-trimethyl-l-cyclohexen-l-ylworin R is water, methyl or ethyl; and

(b) the 2,6,6-trimethyl-1-cyclo-hexen-lyl-vinylucelate formed is hydrolyzed.

3. Process for the preparation of the 2,6,6-trimethyl-1-cyclohexene-lylacetaldehyde used as the main seasoning according to claim 1, characterized in that hydrogen peroxide, an organic Base and / J-ionon are intimately mixed with one another.

The invention relates to seasonings and / or flavorings for food, perfume compositions and perfumed articles, tobacco, chewing gum and medicinal products.

The seasoning and / or flavoring substance according to the invention consists either of 2,6,6-trimethyl-1-cyclohexen-1-ylacetaldehyde (short "ß-Cyclohomocitral") alone or mixed with at least one of the compounds

(i) 2,5-Dimethyl-5-phenylhexen-1-one-3

("Damascol" for short);
(ii) 2,5-dimethyl-5-phenylhexanone-3

("Damascol-4" for short) and / or
(iii) 2,6,6-Trimethyl-l- (but-2'-en-r-oyl) -l, 3-cyclohexadiene ("Damascenone" for short)

and is used to change, modify or improve the taste and / or aroma of the above Substances as well as spices for these substances.

It is the object of the invention to create new solid and liquid seasonings which are capable of a food to give a fruity, woody aroma and / or a wood-tea-like and fruity-tobacco-like taste, the new perfume compositions with woody, catfish, green, earthy, floral and rose-like Fragrance notes produce a sweet, full tobacco-like, flowery, fruity, green, give a woody, "damascnon-like" aroma. The compound called "Damascenon" for short has the following Structural formula:

Its organoleptic properties are described in CH-PS 5 20 479, and earthy notes can

J by using / J-Cyclohomoeitral of the general formula

be achieved. Such a seasoning is suitable for food, chewing gum, medicinal products, perfume compositions, perfumed articles, colognes, types of tobacco and tobacco substitutes.

Other seasoning compositions according to the invention impart perfume compositions and perfumes an:; or an intense and natural rose scent, and you can use it to make perfumed articles that have an intense rose aroma with, if desired, woody, green and earthy notes exhibit. Such seasonings consist of mixtures

(i) one or both of the phenyl-C ₆ -ketones, 2,5-dimethyl-5-phenylhexanone-4 of the formula

The seasonings according to the invention are suitable for Seasoning of solid and liquid products and giving food, chewing gum and medicinal preparations rose-like, fruity, woody and tea-like aromas and woody-tea-like and fruity-tobacco-like Taste notes; Perfume compositions have rose-like, woody, camphor-like, green notes and different types of tobacco sweet, string-tobacco-like, floral, fruity, fresh green, woody and earthy notes, if mixtures of "Damascenon", a Compound of formula

- ¹ Ii and // - Cyclohomocitral of the formula

(hereinafter referred to as "4-Damascol" for short) and / or 2,5-dimethyl-5-phenylhexen-l-one-3 of the formula

(hereinafter referred to as "Damascol" for short) and (ii) ^ -cycloinocitral of the formula

It has been found that the organoleptic effect of the combination of one or both of the foregoing Phenyl-Cb-ketone and ^ -Cyclohoinocitral is stronger than only the sum of the individual organoleptic properties of each phenyl-Cbketons and des fi-Cyclohomocitrals. This effect is called "synergetic" designated.

The general formula of the phenyl C-ketones used in the present invention is

wherein the dashed line is either a carbon-carbon single bond or is a carbon-carbon double bond.

be admitted.

The organoleptic effect of this combination of damascenone and j3-cyclohomocitral is also stronger than simply the sum of the organoleptic properties of the individual components.

According to the invention, the 0-cyclohomocitral which is suitable as a base seasoning, i.e. 2,6,6-trimethyl-1-cyclohexen-1-yl-acetaldehyde, in an expedient manner either

(A) produced in a two-stage process, whereby first / J-ionone with either performic acid, Peracetic acid or perpropionic acid to form / j-) ononenoleester oxidized and then this ester in the presence of a base (aqueous or alcoholic) ur.d hydrolyzes the desired 3-cyclohomocitral is formed, or

ι (B) in a one-step process, where fj-jonon with Hydrogen peroxide is oxidized in the presence of an inorganic base and the / J-cyclohomocitral is formed will.

The method (A) is characterized in that

(i) / i-ionon the fennel

C)

without dimethylformamide with any of the formula

lYTülkansüiirc

wherein R is hydrogen, the methyl or Ällivl-

group is. implemented and /i-.mnonenolcstcr the formula

Il

is formed, and

(ii) this Enolcstcr in the presence of an aqueous or alcoholic base is hydrolyzed to the / i-Cyelohomocilral.

Surprisingly, in this reaction of / J-ionone with a peralkanoic acid in the absence of Dimethylformamide not the expected ß-ionone epoxide r> that has one of the following two formulas:

and or

The oxidation reaction (A) is preferred when a peralkanoic acid is used as the oxidizing agent in the presence of a buffer such as an alkali metal salt a lower alkanoic acid or an alkali metal carbonate with a lower alkanoic acid such as propionic acid, Acetic acid or formic acid. Work is carried out under the following conditions:

(i) Temperatures between 15 "C up to 75 ° C. Lower temperatures slow down the reaction, which also does not go to completion. Higher temperatures result in a lower yield of the desired product and significantly higher percentages of by-products. The most appropriate temperature is around 25 "C.

(ii) A slight molar excess (from about 10 to 15%) of peracetic acid gives a somewhat higher yield. A large excess (around 200%) however, causes the formation of dihydroactinodiolide of the formula

ren inert solvent used, will ,, So ι .nipkweise Cyelohexan or (h;. oroform

!, Ϊ SiSic noticeable effect on

the yield; ^ _ ^ ^ _rf _ _{h wcnn} ^

η conditions through-

^diC ₍ f ^USb Men _E e η by-products formed: larger amount of Ne £, _{lformarnide than}

df SWV] onone _P ox, d

wfrd.

the formula

■ · nrMenee formed by about 70 to 75%, so Care must be taken that the Ri ^ dimethylformamide runs off

^P ß [ononcpoxide. Perbenzoic acid also leads to the formation of the epoxide.

ionon at 25 ° C and to form the corresponding

^de _D eröSoneno.ester is preferably mn! 0% Alkal metaHhydroxyd (beispielswe.se Ka .umhydroxyd. iithi mnydroxyd or sodium hydroxide mixed mn Ä S.wäßrigen Methanoi hydro ys.ert. On the other hand Knn under other mild Hydrolys.crbcd.nnn as aqueous Potassium carbonate, sodium carbonate and carbonate solution. Through this hydrolysis, the desired p-Cycloho-Ta ^ rSSne'Rcaktionsproduk. Is crude / i-Cyclohomocitral, which can be obtained by standard methods, for example by preparation, vc gas chroma extraction , Distillation and dergle.chcn

O'

in an amount of about 30 to 35% yield if no buffer, e.g. potassium acetate in the response rate is available;

(iii) Sodium acetate buffer instead of potassium acetate gives essentially the same yield;

(iv) On the other hand, the yield is somewhat lower when sodium aclate is used instead of potassium acetate is added as a buffer;

(v) If formic acid is used instead of acetic acid in the reaction mass, reduced the yield;

(vi) In this first Oxydalionsreaktion with alkanoic acids may be any over Peralkansäu-,) when hydrogen peroxide (used as Oxydationsm.ttel in the presence of a base panic •) _wl rd ^g is the /J-Cyc.ohomocitral in a mare from the ß-ionone educated. It is made with about 10 to 5 ° hydrogen peroxide. The inorganic base can be an alkali metal hydroxide or an alkali metal carbonate. like sodium, potassium or L.th.umcarbon or sodium, potassium or luhium hydroxide, sodium hydroxide is preferred. The molar ratio of hydrogen peroxide to ß-ionone is

about 11: 1 to 3: 1. ,.

The above procedures are directed to 0-ionon au. Tests have shown that by using sound, "ionone (instead of 0-ionone) epoxy w.rd formed under the ^d u" LI _"e ne conditions and wedeVeine" substantial amount Enolaceta. Still isomers of / J-Cyclohomocitral obtained

With the 2.2.6-TnmethyM-cyclohexen-1-ylacetaldehyde according to the invention, short. called jS-Cyclohomoctral taste and aroma notes can be different -

window products modified, changed, improved or are lent and / or reinforced at all. The seasonings according to the invention have better ones Flavors than many of the well-known fruit and berry flavors as well as tobacco spices. Also can with the ß-cyclohomocitral according to the invention certain fragrances are given, which are usually missing in many perfumes, for example Petitgrain scent, rose scent, lily of the valley scent and Bite scent.

In addition, mixtures of damascenone and 2,2,6-trimethyl-1-cyclohexene-1-acetaldehyde (/ 3-cyclohomocitral) a seasoning is formed which is known to be superior to seasonings and is capable of these seasonings to give new taste and aroma notes and to supplement or improve existing ones. This subheading includes fruit, wine and fermented seasonings as well as tobacco herbs. Also are suitable These mixtures are also used for perfumes or perfumed articles in order to fill these missing scent notes, for example Rose scent to bestow.

The weight ratios of damascenone to β- cyclohomocitral can be 1:99 up to 99: 1, although in practice a ratio of damascenone to β-cyclohomocitral of about 1:20 to about 1: 1 is preferred. The most economical and organoleptically most appropriate range is about 1:20 to about 1:10.

When ß-cyclohomocitral or mixtures of damascenone and / J-Cyclohomocitral used as seasoning additives for food, nature must also the other components are taken into account in the manufacture of the finished food.

By "change" and "modify" is meant that mild, relatively tasteless Substances given certain taste and characteristic aroma notes or already present. Spicy notes are reinforced or supplemented and thereby the quality, character and / or taste of the food flavoring product can be modified.

The term "enhanced" means that one or more flavor and / or aroma nuances that already the organoleptic impression of a product such as food, tobacco, chewing gum, medical Determine product, perfume composition or perfumed article, be intensified without however, this changes the quality type of the aroma or taste.

Food includes both solid and liquid edible products, with or without nutritional value, such as soups, ready meals, beverages, dairy products, sugar confectionery, vegetables, cereal products, non-alcoholic Drinks, light snacks and the like.

Chewing gum is a mass of an essentially water-insoluble, chewable, plastic gum pulp, like chicle or a substitute like jelutong, guttakay gum and / or certain natural ones or synthetic resins or waxes and plasticizers such as glycerin and a condiment. as Seasoning is suitable / J-Cyclohomocitral or a mixture of this compound with Damascenone.

Medical preparations are solid or liquid per os products to be taken such as cough syrups, cough drops, toothpastes, aspirin and chewable medical tablets.

Substances used as additives or seasoning aids can be used are known and sufficiently described in the relevant literature. she are "edible" and neither toxic nor harmful in any other way. However, it is essential also that such additives are organoleptically compatible with ß-Cyclohomocitral or with Mixtures of damascenone and 0-cyclohomocitral. Furthermore, these additives must be stored in the storage conditions and when used at room temperature inert towards damascenone and 0-cyclohomocitral be.

Such seasoning auxiliaries or carrier substances include, in the broadest sense, stabilizers, thickeners, Wetting agents, conditioning agents and other seasonings and seasoning enhancers. You can either be solid or liquid, their consistency depending on the desired aggregate state of the end product is and they must with the ß-Cyclohomocitral or its mixture with damascenone be homogeneously dispersible or miscible.

The amount of ß-cyclohomocitral or its mixture with damascenone can vary in a relatively wide range and is based on matched the end product. An excess should be avoided, since too large an amount is unnecessary Causes costs and in extreme cases disrupts the taste-aroma balance.

In general, the added amounts of ß-cyclohomocitral are or its mixture with damascenone to form foods in the range of 0.2 parts / mill. up to about 50 parts / million based on the total weight of the composition. Concentrations above 50 Share / Mill. in most cases do not have an improving effect on the organoleptic properties.

Seasoning compositions for foods produced according to the invention contain ß-cyclohomocitral or its mixture with damascenone in concentrations of about 0.1 to 15% by weight, based on the total weight of the seasoning composition.

The seasoning mixes or seasoned products can be produced according to conventional working methods as they are known in batter beating and in the fruit beverage industry. In general the ingredients are simply mixed in a suitable mixer to achieve the desired consistency, Maintain homogeneity of the dispersion, etc. On the other hand, seasoning compositions can be used in Form of crushed solids by mixing / J-Cyclohomocitral, or its mixture with Damascenone, with, for example, gum arabic, fragant gum, and the like, followed by spray drying getting produced. Ready-made seasoning mixes in powder form, for example fruity-flavored powder mixes, are made by mixing the dried solids such as starch, sugar and the like with ß-Cycloho mocilral or its mixture made with Damascenor, this mixture in a dry mix xcr is mixed until the required Grai uniformity is achieved.

The following sausage additives are suitable for combination tion with / J-cyclohomocitral or its mixture with damascenone:

p-hyilroxybene / acetone; C ieraniol, acetaldehyde. Maltol, ethylmethylphenylglyeidate, bunzyl acetate, dimethyl sulfide, vanillin, methylcinnamate,
Ethyl pelargonate. Methyl anthranilate, isoamylaceu

709 BMI / 4

isobutyl acetate, α-ionone, ethyl butyrate, acetic acid, y-undecalactone, naphthyl ethyl ether, diacetyl, ethyl acetate, anethole, isoamyl butyrate, cis -3-hexenol-1; 2-methyl-2-pentenoic acid, Elemecin (4-allyl-1,2,6-trimethoxy-benzene), isoelemecin (4-propenyl-1,2,6-trimethoxybenzene), and 2- (4-hydroxy-4-methylpentyl) norbornadiene.

The seasoning with seasonings according to the invention to improve smoking tobacco is opposite π conventional methods so that certain problems that have arisen up to now are eliminated, especially when producing or enhancing certain wood-flavored characteristics of natural tobacco should be. With the seasonings according to the invention ι the seasoning character can easily be controlled and on the desired uniform level be maintained, regardless of the differences and variations in the Tobacco components in the mixture.

In addition, tobacco additives can also be produced by improved processes, with the Smoking tobacco products desirable wood-spicy characteristics with sweet, flowery, fruity, earthy and green notes that are slightly varied and kept at a consistent level: can. The smoking tobacco or a corresponding substitute (e.g. dried lettuce leaves) a flavoring and seasoning additive is added, the active component either (i) / f-Cyclohomoeitral contains alone or (ii) a mixture of damascnon and / i-cyclohomocitral.

In addition to cyclohomocitral or its mixture with damascnon, other seasoning and flavoring additives can be added to smoking tobacco or its substitute either separately or together with the seasoning according to the invention. Such additives are:
1. Synthetic fabrics:

/ i-Ethyl cinnamaldehyde, eugenol, dipinthine, damascnon, maltol, ethyl maltol, δ-undecalactone, ( ¹ KIeCaIaCtOn, benzaldehyde, allyl acetate, ethyl bulyrate, ethyl valerate, ethyl acetate, 2-llexenol-1, 2. 3-nonadien-8-one, 2, b-dimethyl-2,6-undecadien-IO-one, 2-Met hy I-.5-isopropy / acetophenone, 2-llydroxy-2,5,5,8a-tetrumethyl -l- (2-hydroxyethyl) -deeahydronaphthalene, dodecahydro-Ja, 6,6,9a-teiramelhyl-naphtho- (2, lb) -furan, 4-hydroxy hexanoic acid, gamma-1.actone, polyisoprenoid hydrocarbons, described in Example V of IJS-PS 3 ^r > «9 372.

II. Natural oils:

Sclerosis seed oil, coffee extract, hcrgamot oil, cocoa extract, Nutmeg oil, canned oil. An aroma utul Wür / conccnlral, the / f-Cyclohomofitriil oiler a mixture of Damasccnoii and // - Cyelohoinocitral and, if desired, contains one or more of the above-mentioned / essential seasoning additives, canoe / tobacco itself, / to udder or / u the blue or Papicnimluilluiig can be added. Also a Tobacco substitutes (for example lettuce leaves) or mixtures thereof can be mixed with dom Wür / stoff vciset / i will. The Meiigetiantcile of the Wiirz.-Additives are varies according to the desired result. Is it has been found that satisfactory results are cr / .ieli if this (iewichlsvi ratio of Grand sum of / i-cyclohomocitral or its Mixture with damascenone between 125 parts / mill. and 1500 parts / mill. (0.0125% to 0.15%) of the active ingredients in smoking tobacco. For one Seasoning has a weight ratio of the total of / J-Cyclohomocitral or its mixture with damascenone between 1000 and 10 000 parts / mill. (0.10% to 1.5%) proved to be satisfactory.

The seasoning can be incorporated into the tobacco product in any conventional manner, for example dissolved in an appropriate solvent such as ethanol, pentane, diethyl ether and / or other volatile organic solvents. The solution obtained is either on the prepared Tobacco is distributed or the tobacco is immersed in the solution. Under certain conditions, the appropriate solution is brushed onto the wrapping paper or the wrapping sheet of the smoking product or rolled on or either sprayed on, dipped or coated on the filter will.

Furthermore, it is possible to treat only part of the tobacco or the substitute and that which is seasoned in this way Tobacco can be mixed with other tobacco components before the end product is manufactured. In In these cases, the treated tobacco content contains an excess of seasoning, the concentration being so it is selected that the specified percentages of seasoning are present in the end product. "An aged, pickled and shredded house tobacco can do one with a 10% ethyl alcohol solution 1:! Mixture of damascenone and ß-cyclohomocitral be coated in an amount sufficient to obtain a tobacco composition containing 400 parts / r> Mill., based on the weight of ji-cyclohomocitral-damascenone mixture Contains on a dry basis. The alcohol is evaporated and the tobacco is processed into cigarettes using conventional working methods. A cigarette produced in this way has a desired in and pleasant aroma which when smoked in the I latipt and side streams can be seen. This aroma can be described as sweeter, rich, less strict, more tobacco-like and has excellent woody properties "Cigar boxes" notes.

Γι Another preparation is that eir Aged, pickled and shredded house tobacco with a 20% ethyl alcohol solution from fi-Cyclohoinoci is coated in such an amount that the tobacco / oil composition is 800 parts / million, based on • 'ι the weight of / i-Cyclohomoeitral auf Troekenbasii adheres to. Cigarette made from this tobacco! have a pleasant aroma that when smoked in I laupistrom and the tributaries are also noticeable around the sweeter, rich, less strict, tobacco-like ■ 'with hol / like and damascenonar notes.

The seasonings according to the invention are suitable

especially / ur production of smoking tobacco, vvi

Cigarette, cigar and pipe tobacco. But c

can also produce other tobacco products

'"covered or compressed tobacco dust or tobacco

Abrasion can be treated with I ¹ IrToIg. Furthermore, the working material can be used to make the filter tip

rial, the nalitpasle, the packaging material and

like substances that are used in the preparation of a

'■' Smokers' products are used, admittedly.

l'.'ne other group of products starting with 'Ie

cifindiingsgemalkn Würzsloffcn will be improved can are perfumes and Parfümarlikcl. / i-t'yclohoiiu

Il

citral can be mixed with one or more perfume additives, for example alcohols, aldehydes, nitriles, esters, cyclic esters and natural essentials oils are mixed so that the combined fragrance notes of the individual components have a pleasant and result in the desired fragrance, in particular flower, rose, lily of the valley or petitgrain fragrance.

Such perfume compositions usually contain (a) the main note, flower or that "Bouquet" or the cornerstone of the composition; (b) Modifiers that round off the main note and accompany; (c) Fixatives, which comprise fragrance substances which the perfume during all stages of the Give evaporation a special touch, as well as substances that delay evaporation; and (d) Top notes, which are usually low-boiling, fresh-smelling substances.

With / J-Cyclohomocitral the aroma characteristics a perfume composition can be changed. For example, by taking advantage of or mitigating the odor response of another component of the composition.

The effective amount of the ß-cyclohomocitral in Perfume compositions depend on many factors, especially the other ingredients present, their amount and the desired effect. It has been found that perfume compositions that only 0.1% or less (/. B. 0.05%) jS-cyclohomoeitral contain, already enough to make soaps, cosmetic and other products earthy, woody, green as well as flower and rose notes or existing earthy, woody, fresh-green, Change, modify or intensify notes of flowers and roses. The amount used can be up to 10% of the fragrance component and depends on the cost, the nature of the end product, the desired Effect and the particular fragrance you are looking for.

The / J-cyclohomocitral can be used either alone or in Perfume compositions as an odor component in wetting agents and pages, room sprays, deodorants Agents, perfumes, cologne, toilet water, bath preparations such as bath oils and bath salts, Hair preparations such as hair sprays, brillantines, pomades and shampoos; cosmetic preparations such as creams, Deodorants, hand lotions and sunscreens, powders such as talc, dusting powder, face powder and the like can be used. It is sufficient 1% / i-Cycluhomocitral, to give petitgrain preparations a fresh green, earthy note. 4% / l-cyclohomoeitral are sufficient to make flower or lily of the valley preparations to add or enhance a rose note. Generally used for perfume compositions no more than 10% / i-cyclohomoeitral required in relation to the finished end product.

Furthermore, a mixture of Damascol (phenyl Ci, ketone) and / i-cyclohomocitral and one or more Perfume auxiliaries, for example alcohols, aldehydes, Nitriles, esters, cyclic lister as well as natural essentials Oils / ugemischl are so that the combined Scents of the individual components produce a pleasant and desired scent, in particular and preferably in rose, lily of the valley and other "blossom" fragrances.

The effective amount of the mixture of Damascol and / J-Cyclohomocilral in perfume / ointments / ungcn also depends on many factors, including other ingredients, their amount and effect. It it was found that an amount of only 0.01% and even less (e.g. 0.005%) are enough to give cosmetic or other products a rose or lily of the valley fragrance to rent. The seasoning mixture can be added in an amount of up to 10%.

The mixture of Damascol and Jj-Cyclohomodtral can be used alone or in perfume compositions as a fragrance component in the same way and for the the same cosmetic and hygiene products as ß-Cyclohomocitral are used. As an odor component 1% of the Damascol - /} - cyclohomoeitral mixture is sufficient, to give petitgrain preparations a green, earthy note. Generally no more than 3% of the mixture, based on the finished end product required in the perfume compositions.

It was found that the weight ratios of Damascol (phenyl-CVketone) to ß-Cyclohomocitral of 1: 5 to 5; 1, suitably about 2: 1 up to about 4: 1 are useful.

The mixture of Damascenone and ß-Cyclohomociiral behaves similarly to ß-cyclohomocitral. It was found that already 0.01% and even less (z. B. 0.005%) of the Damascenon-jä-Cyclohomocitral mixture Soaps, cosmetic or other preparations have a rose aroma with earthy and fresh green notes to lend. The added amount of the seasoning can be up to 10%.

The mixture can be used alone or in perfume compositions as an odor component during preparation the toilet, cosmetic and hygiene articles mentioned above are used. As an odor component 1% of the Damascenone / JCyclohomocitral mixture is sufficient, to give lily of the valley preparations an intense rose scent. In general no more than 3% of the seasoning mixture is required.

The perfume or fragrance compositions can be a carrier or a carrier nutrient! for either (i) fJ-cyclohomocitral alone or (ii) the phenyl-Cn-ketone - /} - cyclohomocitral mixture, or (iii) contain the damascenone - /? - cyclohomocitral mixture. The carrier can a liquid such as an alcohol, a non-toxic alcohol, a non-toxic glycol, or the like be. However, it can also be made of an absorbent solid such as gum (e.g. gum arabic), or a substance suitable as a capsule, such as gelatin.

The invention is further illustrated by the following examples wherein Examples 1, 2,4-8, 10, Il mid illustrates Ii-1 ^r> manufacturing method of the suitable erfindungsgemiiß / f Cyelohomoeitrals. Example ¹ ) / the like, since dimethylformamide cannot be used for the purposes of the invention in the oxidation of / ionone with peracetic acid. Example i / the like, if a reaction without a buffer, /. B. sodium acetal, does not / leads to desired result. Example 12 shows that when λ-ionone is used instead of / i-ionone, the desired [\ - | oiionenoller is not formed. The examples lh 30 / show the usefulness of the / i-Cyclohomocilral per se as well as the Damascol;! C '\ cloluimocitral- and the Damascenon,' / ■ (. 'Yclohoniocitral mixtures.

All quantities and pro / cniangabeu are (irwu histei Ie. if nothing else said lsi.

Be ι s ρ u-l I

<V 11 c rs I el Ii Ii ic from / (■ Ionone Holest er from / (Ionon
one with a stirrer. I heniiomeier. RiiikHullkiihlei, ■ ichler and Kiihlbad equipped 2 I.Her

The following ingredients were added to the reaction flask:

(i) solution of 96 g] ϊ- | οηοη in 300 ecm chloroform;
(ii) 30 grams of sodium acetate.

95 g of a 40% strength peracetic acid were then slowed down for one hour with cooling at 10 ° C admitted. The reaction mass was stirred for an additional hour at 10 ° C. and then the solution was slowly stirred warmed to room temperature. The reaction mass was then poured into 1 1 of water and the obtained organic and aqueous phases separated. The aqueous phase was with 100 ecm chloroform extracted, and the organic phases obtained were combined. After evaporation of the Solvent from the organic phase were obtained 99.5 g of an oil on 1000 g of aluminum Chromatographies, deactivated with 5% w / w water and eluted as follows:

Fraction Vol.-Lösmille I

(ecm)

Amount of
eUiiierlem.
solved SloiT

lg »

1 ~ 50 hexane SO

2,500 hexane 31

3,300 hexane! 3.5

4250 hexane 7.0

5 250 hexane L ¹⁵
Ο 240 hexane Ld

(> 00 25 ¹ V Diälhx lather 15.d

75 "'ii hexane

S M> 0 Diiithvläther! 5 ^

The fractions Ί to 4 consisted essentially of / i-Jononenolester.

The spectral data of a purified sample of this material (obtained by preparative gas chromatography and mass spectrography as well as IR and NMR spectrum) confirmed the structural formula

(K

B. Hydrolysis to form / J-Cyclohomocitral
from / i-ionic olestcr

60.2 g of jS-ionic ester, dci fractions 1 to 4 from Step (A), 280 ecm of 10% potassium hydroxide solution (in a 50:50 water / methanol mixture) at room temperature and 30 minutes touched. Then 1000 ecm of water were added to the Given the reaction mass, which was then extracted with three 250 cc portions of diethyl ether. the The combined ether extracts were mixed twice with two 100 ccm portions of saturated sodium chloride solution washed, dried over anhydrous magnesium sulfate and evaporated. There were 53 g of one Obtained oil that was jS-cyclohomocitral.

The crude / J-Cyclohomocitral was distilled at 2 mm Hg pressure and the fraction boiling at 70 to 80 ⁼ C fraction was collected. It was 35.6 g.

Gas chromatographic analysis showed the product to be about 85% pure. A pure sample of the / i-cyelohomociiral was obtained by preparative chromatography. The conditions were: a 10 'χ V ₄ "10% water-soluble polyethylene glycols column filled stainless steel at 220 ^r C isothermal studies by mass spectral, IR and NMR analyzes showed the following structural formula.:

B e ι s ρ ie 1 e 2 to IO

The same process steps as in Example 1 were used in the following examples. They show the fist. which occur when parameters of the oxidation reaction of ft- ionone with peracetic acid are varied, for example with regard to the buffer, the solvent, the temperature. Presence of organic base and ratio of organic alkanoic acid to peracetic acid. The percentages were obtained by gas chromatography analysis of the reaction mixture after 30 minutes and do not represent the yields of isolated masses

l'nolesler

material

IMOtlllkll "

-3

iscv / un

ipicl

Knolester

Source material

40

52

31

49

36

29

26th

30th

21

17 by-products

91
/ f-ionone epoxide

16

Respondents

and reaction conditions

Cyclohexane (150 ecm) sodium acetate (20 g) jS-ionone (30 g)
40% igc peracetic acid (30 g) Temperature: 25 C

Acetic acid (150 ecm) potassium acetate (35 g)
/ J-Jonon (30 g)
407 ° peracetic acid (30 g) Temperature: 25 C

Formic acid (150 ecm) potassium acetate (50 g)
jß-Jonon (30 g)
40% peracetic acid (30 g) Temperature: 25 ° C

Acetic acid (150 ecm) potassium acetate (35 g)
j8-ionone (30 g)
40% peracetic acid (33 g) Temperature: 25 "C

Acetic acid (150 ecm) potassium acetate (35 g) ./i-Jonon (30g)
40% acetic acid (33 g) temperature: 50 ° C

Dimethylformamide (150 ecm) ./i-Jonon (30 g)
40% peracetic acid (33 g) Temperature: 4 days at 18 ° C

Acetic acid (450 ecm) potassium acetate (105 g) jß-ionone (96 g)
40% peracetic acid (105 g) temperature: 25 ° C

Example 11

Production of ß-Cyelohomocitral by
HjCh peroxidation of /? - ionon

12 ml of 30% strength hydrogen peroxide were added to 20 g of β-] onone in 100 ml of methanol. The solution was cooled to 15 ⁰ C and aqueous sodium hydroxide 6molar added over 30 minutes. The reaction mixture was kept at 15 ° C., then allowed to warm to 30 ° C. and kept at this temperature with external cooling. The exothermic reaction lasts about 60 minutes. An examination by gas chromatography showed that some β-] onone was still present in the reaction product. An additional 12 ml of 30% hydrogen peroxide and 18 ml of 6 molar aqueous sodium hydroxide were added over 30 minutes, the temperature being maintained at 25 ° C. The exothermic reaction lasted again for about 60 minutes and the temperature was kept at 30 ^° C. during this time. The reaction mass was then poured into excess water (500 ml) and the product extracted with three 150 ml portions of diethyl ether. The combined ether extracts were then washed with two 150 ml portions of saturated sodium chloride solution and dried over anhydrous MgSC> 4. The solvent was evaporated and 16.8 g of a crude oil remained.

Examination of this oil by gas chromatography showed 22% iS-cyclohomocitral.

The desired product was obtained by preparative gas chromatography (in a 10 'χ' / <"10% water-soluble polyethylene glycols, column filled stainless steel at 220 ⁰ C isothermal). The structural formula

was determined by IR, mass spectrographic and NMR analyzes confirmed.

709 550/422

25th

Example 12
Formation of Λ-ionone epoxide from (X-) onone

In a 500 ml flask equipped with a thermometer, stirrer, filling funnel and reflux condenser, ~> the following components are introduced in the order given:

Components

Menno

acetic acid bü ecm Potassium acetate 35 g ff-Jonon 30 b

Then 33 g of 40% peracetic acid was added dropwise added with stirring at 25 ° C. within 45 minutes. The reaction proceeded for one hour exothermic and was then left to stand at room temperature for 15 hours.

The reaction mass was then poured into 500 ml of water and the product in three 150 ccm portions Diethyl ether extracted. The ether extracts were combined and with two 100 cc servings saturated sodium chloride solution and then dried over anhydrous magnesium sulfate. The oil obtained after stripping off the solvent was at 94 to 99 ° C and a pressure of 0.5 mm Hg distilled and gave 28.3 g of a pure, colorless liquid.

The IR, mass spectrum and NMR analyzes showed that the compound obtained was a-] onone of the formula

O
was.

Example 13
Manufacture of / J-Cyclohomocitral

In one with a stirrer, thermometer, filling funnel and 2-1 reaction flasks equipped with a cooling bath were as follows Components introduced in the order given:

Components

\ Narrow

acetic acid

Potassium acetate

/ i-Jnnon

624

450 ecm
150 g
96 u

Then 105 g of 40 "/ 0IgLT pressigic acid was added dropwise added with cooling, while the reaction mass was held at 25 C ± 2 "C" for 2 hours. The reaction mixture was then wum-rc uici Stirred at 25 ° C. for hours. A slightly exothermic reaction was observed during the first hour.

The reaction mixture was then poured into 100 ml of water and the product obtained with three 300 ecm volume of diethyl ether extracted. The ether extracts were combined and with two Washed iSO cc portions of saturated sodium chloride solution. The washed ether extract obtained was evaporated to give 118 g of an oil.

In 400 ecm '»0% potassium hydroxide solution (50:50 mixture Water to methanol) 118 g of this oil were added. The solution warmed up slightly and became Stirred for 45 minutes.

The solution was then poured into 500 ml of water and the mixture in three 250 cc portions Diethyl ether extracted. The diethyl ether extract was mixed with two 200 cc portions of sodium chloride solution washed, dried over anhydrous magnesium sulfate and evaporated. There were 89 g of a crude oil obtain. This is distilled through in a Vigreux distillation column at 70 to 74 ° C and 2.0 mm Hg pressure and gave 40.2 g of a compound of the formula:

II

as determined by IR, NMR and mass spectral analyzes.

Example 14

Perpropionic acid was prepared as follows: A mixture of

160 ml propionic acid

1 ml sulfuric acid (concentrated)
40g of 50% hydrogen peroxide

herein as
»Mixture Λ <· denotes

was allowed to stand at room temperature for 20 hours.

The following compounds were placed in a 500 ml reaction flask equipped with a stirrer and cooling bath brought in:

140 ml propionic acid
75 g potassium acetate
60 g / i-ionone

herein as

"Mixture

designated

To this mixture B, mixture A was added dropwise over 60 minutes and the reaction temperature was kept at 25 ° C. ± 2 ° C. by external cooling held. After the addition was complete, the reaction mixture was stirred at 25 ° C. for a further 2 hours.

Then the reaction mixture was poured into 1000 ml of water and with two portions of 250 ml of diethyl ether extracted. The combined ether extracts were then first washed with water (three 100 ml portions) and then washed with a saturated sodium chloride solution (150 ml). The ethereal solution was over dried anhydrous magnesium sulfate and the solvent evaporated. Thereby, 78 g of a Obtained crude oil that contained propionic acid as well as product. The crude product was made with a solution 40 g of potassium carbonate in 300 ml of water are hydrolyzed for 15 hours by refluxing, with Was stirred manually. After cooling, the organic layer was collected and the aqueous layer extracted with 200 ml of diethyl ether. After combining the organics, it became the solvent evaporated to obtain 57.5 g of an oil. This was distilled to give 19.5 g of β-cyclohomocitral (Yield: 37%).

Example 15

(4% I.

(41%)

(32%) other products 23% trals was obtained by preparative chromatography. The formula is:

Peranic acid was produced as follows:

20 g of 50% strength hydrogen peroxide and ro ml of formic acid were mixed with one another and this Reaction mixture P / 2 hours at room temperature ditched.

The previously used was added to a mixture of 50 g of potassium acetate, 70 ml of fatty acid and 30 g of I-ionone h performed performic acid was added dropwise over 30 minutes. It was stirred and the Temperature kept at 25 ° C by external cooling. After the addition was completed, the mixture became

Stirred for a further 90 minutes at 25 ° C. and then poured into 800 ml of water. This product was washed with two? 00-ml portions of diethyl ether extracted, the zusamegebenen r £ _x t _ra kte with two 150 mL portions of ^m ättigter Natriumchlondlösung washed and then dried ^. After the solvent had evaporated, 32.5 g of a crude oil remained

Gas chromatography analysis revealed the following compounds:

and the mass spectral as well as IR and NMR analyzes confirmed this formula.

Example 16 Raspberry flavor

The following basic mixture for a HJmbeer seasoning was prepared:

Parts by weight

Components

2.0 5.0 5.0 2.0 6.0 16.0 1.0 13.0 10.0 10.0 930.0

The following mixture was produced:

20 g lithium carbonate
200 ml of 50% aqueous methanol

"And then the crude enol ester is added. This The reaction mixture was then heated to 65 to 70 ° C until the hydrolysis of the enol ester to ji-cyclohomocitral essentially ended. This was confirmed by gas chromatography. After adding The reaction mixture with three 200 o.m poruons became smarter Diethyl ether extracted. The combined ether extracts were twice with two 100 cc servings of saturated sodium chloride solution washed, dried over anhydrous magnesium sulfate and evaporated to an oil. d. H. / l-Cyclohomocitral to obtain.

The crude product was distilled at 2 mm Hg pressure and the fraction boiling at 70 to 80 "C

collected. .

Gas chromatography analysis showed a purity of about 85%. A sample of pure 0-cyclohomoci vanillin

Maltol

Parahydroxybenzyl acetone

<x-] onone (10% in propylene glycol)

Ethyl butyrate

Ethyl acetate

Dimethyl sulfide

isobutyl acetate

acetic acid

acetaldehyde

Propylene glycol

Part A

J3-Cyclohomocitral became half of the above The so-called C-round mix was added in an amount of 0.2%. This mixture was made with the master batch without ß-cyclohomocitral compared, where 0.01% (100 parts / mill.) In water examined and carried out investigated a test stand committee. 11 The / J-Cyclohomocitral The mixture containing it had a far more pleasant and better raspberry aroma than the preparation without this seasoning. It was the unanimous opinion of the committee that the chemical compound ß-Cycloho -, -. mocitral the aroma, the taste and the fragrance, in short the spice rounds off and a very natural, contributes to the fresh aroma and taste found in fully ripe raspberries.

part B

Three servings of the above base mix were made and each one with the following Connections staggered:

a. Damascenone, 0.01 part / mill .;

b. /j-Cyclohomoeitral.O.I parts / mill .; and

c. Mixture of 0.01 parts / mill. Damascenon and 0.1 Parts / mill. ^ -Cyclohomocitral.

The mixture of damascenone and / J-cyclohomocitral as such is sweeter, fruity, fruity-rose-like and more pleasant in taste and aroma than / J-Cyclohomocitral or Damascenon aiicin if the πι compounds at a concentration of 10% in Ethanol solutions are examined.

The three mixtures were examined by members of a review board, each

! "hurry / garbage. in water. The majority of the members of the Committee preferred the spice composition, which is the mixture of Damascene :! and / J-cyclohomocitral contained and referred to this as the most natural raspberry seasoning, as it is the only composition which has the characteristic aftertaste of ripe raspberries.

The addition of the mixture of damascenone and jJ-Cyclohomocitral to the base seasoning results in a unexpected and surprising effect as only 50% of each egg requires constituents of the mixture is used to maintain the same strength of flavor and aroma notes expected when only the starting compounds themselves are examined organoleptically.

Similar results would be obtained with the following weight ratios of damascenone and β-cyclohomocitral achieved:

Damascenon / f-Cyclohomocitral Weight 20th relationship 6.7 Parts / mill. Tcilc / Mill. 5 0.05 1.0 1 4th 0.15 1.0 1 2.5 0.20 1.0 1 1.7 0.25 1.0 1 1 0.4 1.0 1 0.6 1.0 1 1.0 1.0 1

Example 17

2 parts / mill. a 1: 1 mixture of damascenone and jJ-cyclohomocitral was added to burgundy and compared to an unseasoned wine by a board of examiners. The flavored wine was made preferred because it had several top notes and a richer aroma, giving the impression of a "Round" and "aged" wine was created.

Example 18

A mixture of 3 parts by weight ß-Cyclohomocitral and 1 part by weight damascenone were added to distilled white vinegar in an amount of I) OI _1% and compared in water (in an amount of 1%) with ungewürztem vinegar. The spice mix gave the distilled white vinegar natural top notes similar to wine vinegar and rounded them off, improving the aroma and taste of this product.

Example 19

Part 1
(A) Powder seasoning

20 g of one of the seasoning compositions from Example 16, Part A or Part B, each of which contained jS-cyclohomocitral, were emulsified in a solution of 300 g of acacia resin and 700 g of water. This emulsion was spray-dried (inlet air stream having a temperature of 260 ⁰ C and an outlet temperature of 93 ° C and 50 000 r / min.).

(B) Paster mixture Then the following mixture was made:

Components

Liquid seasoning composition according to Example 16 (Part A or Part B)
Silica

Characteristics:

Surface area: 200 m ^2,
Nominal size of the particles: 0.012 μ, density: 0.01068 g / ccm

Parts by weight

48.4 3.2

The silica was dispersed in one of the mentioned liquid seasoning compositions with vigorous stirring. 48.4 parts by weight of the powder produced in part (A) of this example 19 were ^{stirred into the viscous liquid obtained in this way at 25 °} C. for 30 minutes. The result was a thixotropic, uniformly flavoring paste.

Part II
chewing gum

100 parts by weight of chicle were mixed with 4 parts by weight of one of the seasoning compositions according to Part 1 mixed in this example 19 and then 300 parts sugar and 100 parts corn syrup added and the whole intimately mixed. The gum mix was cut into strips. It had a pleasant, long time persistent raspberry flavor.

Part III
Toothpaste

The following separate groups of mixtures were made:

Group "A"

30,200
15,325

■ π .100

.125
.400

Group "B"

-, o 12,500
37,200

Group "C"
2,000

Group "D"
1,200

100.00 (total)

Glycerin

distilled water sodium benzoate saccharin sodium stannous fluoride

Calcium carbonate dicalcium phosphate (dihydrate)

Sodium n-Lauroyl Sarcosinate (foaming agent)

One of the seasoning compositions from Part I.

Procedure:

1. The ingredients from group "A" were stirred in a vessel provided with a steam jacket and heated to 71 ° ^C;

2. It was stirred for a further 3 to 5 minutes until a homogeneous paste was formed;

111

3. The powders from group "Β" were added to the gel and the whole thing to a homogeneous one Mix the mass;

4. While stirring, the seasoning compositions from group "D" and finally the sodium n-Lauroyl Sarcosinate ("C") added;

5. The resulting slurry was then mixed for 1 hour. The finished paste was homogenized and used for Finally filled in a tube.

The toothpaste thus obtained had a pleasant raspberry taste with normal use constant strong intensity.

Part IV

Chewable vitamin tablets

One of the seasoning compositions of Example became a chewable vitamin tablet in one Amount of 5 g / g given. The vitamin tablet consisted of the following components;

g / 1000 tablets

Vitamin C (ascorbic acid) as

Ascorbic acid-sodium ascorbate mixture 1: 1

Vitamin Bi (thiamine mononitrate) Vitamin B2 (riboflavin)

Vitamin Bt, (pyridoxine hydrochloride) Niacinamide

Calcium pantothenate

Vitamin Bi2 (cyanocobalamin)

Vitamin E (di-a-tocophenyl acetate) d-biotin

Muted dye

One of the seasoning compositions from Example 16

Sweetener (sodium saccharin)

Lubricant (magnesium stearate)

Mannitol (for baking)

When chewed, these tablets had a pleasant, long-lasting, strong raspberry flavor that Sustained constant for 12 minutes.

Example 20 Tobacco Composition

A tobacco blend was made from the following ingredients:

Components

Maltol

Cocoa extract

Coffee extract

Ethyl alcohol

water

Weight lcile

2.00 26.00 10.00 20.00 41.90

Part A

70.0

4.0

5.0

4.0

33.0

11.5

3.5

6.6

0.044

5.0

5.0

1.0

10.0

500.0

Components

Bright

Burlcy

Maryland

Turkish

Stcn (fire-dried)

Glycerin
water

Parts by weight

40.1 24.9

1.1 11.6 14.2

2.8

5.3 This seasoning composition was used in an amount of 01% to all of the above tobacco blend manufactured cigarettes. Half of the cigarettes were then with 500 or 1000 Te.len / M.ll. fl-Cyclohomocitral. manufactured according to example 1 or 13. treated. These cigarettes and those without ß-Cyclohomocitral were compared in pairs: it was found that the test cigarettes had more fullness and at Smoking sweeter, richer, more tobacco-like and less stringent and woody, damascenon-like notes exhibit.

Before smoking, the tobacco used in the test cigarettes had a sweet, floral, fruity, earthy and fresh green note. All cigarettes were fitted with a mm cellulose acetate filter.

The fl-Cyclohomocitral, produced according to Example 1 or 13, enhances the tobacco-like taste and that Aroma and gives the cigarette made with it a woody, damascenon-like note.

part B

The tobacco wort described above was added in an amount of O, l ^ll / o on all of said cigarettes manufactured tobacco blend. The -. Half of the cigarettes were then treated with 250 or 500 parts per mill of a mixture of 0.1 part damascenone and 1 part β-cyclohomocitral. These cigarettes have been compared to unseasoned cigarettes.

In the cigarette containing the seasoning composition

... rescues had more abundance and were smoking

sweeter richer, more tobacco-like and less severe than that

unseasoned cigarettes and keep an intense

woody and fruity note. . .

The tested cigarettes were all with one η 20 mm cellulose acetate filter fitted

The seasoning mixture from Ö-Cyclohomocitral unc Dmiascenon therefore enhances the natural tobacco irtieen taste and aroma of a cigarette unc gives it a holy and fruity feel when smoking.

'" Grades. .

Example 21

Petitgrain Composition

Cigarettes were made from this tobacco. The seasoning composition for this consisted of:

Components

Ethyl butyrate
Ethyl valcrate

Parts by weight

0.05 0.05 components

fl-Cyclohomocitral

according to example 1 or 13

Linalool

Linalyl acetate

Dimethylanthraniite

Terpincol

Gcraniol

Terpinylaietai

Geranyl acetate

Ocimcn

Unions

Pinene

Ncrolidol

Part by weight

20th

500

600

20th

30th

10 5

20th

50

20th

IO

7 (1Q Hütl / Ü

The / J-Cyclohomocitral gave the Petiigrain the the green, earthy note required for this.

Example 22 Lily of the Valley Perfume The following ingredients were mixed:

Components Parts by weight lndol 2 Hexylcinnamylaldehyde 400 Rhodinol 40 Terpinol 30th Tetrahydro-2-pentylpyran-4-ylacetate 10 Cinnamyl acetate 5 4 (4-hydroxy-4-methylpentyl) -3-eyclo- hexene-1-carboxaldehyde 20th Hydroxycitronellal 280 Violet leaves absolute (10% in Diethyl phthalate) 4th Phenylethyl alcohol 45 Tetrahydromuguene 20th n-Undecylenealdehyde (10% in diethyl phthalate) 5 n-decanal (10% in diethyl phthalate) 5 n-nonanal (10% in diethyl phthalate) 4th Benzyl acetate 10 Dimethylphenylethylcarbinol 10 p-t-butyl-ft-methylhydrocinnamyl- aldehyde 4th Methyl cinnamate (10% in diethyl phthalate) 2 Benzyl cinnamate 4th

Components

b-Oxa-l, l, 2,3,3,8-hexametal-

2,3,5,6,7,8-hexahydro-1 H -benze [f] -indene 4'-t-Butyl-2 ', 6'-dimethyl-3'-5'-dinitroacetophenone

p-t-butyl-ivinethylhydroaminamylaldehyde

Diethyl phthalate

Clewichtieilc

550 450

20 90

6230

35 parts by weight of a 10% solution of p-Cyclohomocilral (according to Example 1 or 13) m

ι, diethyl phthalate added. This connection bestowed the mixture has a rose effect, which is achieved by adding a further 35 parts by weight of the 10% strength jS-Cyclohomocitrallösung has been significantly strengthened. A further improvement in the rose effect was achieved through additional

. '"Ι achieved before 35 parts by weight of the solution.

Example 24 Rose scent

940

40 parts by weight of a 10% solution of / J-Cyclohomocitral (according to Example 1 or 13) in diethyl phthalate were added to the above mixture. The / J-cyclohomocitral improved the flower nuance and significantly increased the rose character of this lily of the valley fragrance.

In another experiment, 80 parts by weight of a 10% strength solution of the / j-cyclohomocitral were added. The nuance of the flowers has been considerably improved and the character of the rose has been enhanced.

Example 23 (Jewi Blood Iparfiim W) To a mix of 370 lestandleile 500 Lavender type Barreine 120 l.inalool 520 Phenyl ethyl alcohol WHERE Benyl acetate l.inalylacolate K) (I. I lyilroxycilronelUil 2 30 4 (4-Hydroxy 4 nieihvlpentvl) - 1 c \ clo K) OO hexen-1 -caibo \ aldch \ d 120 l'lugenol 5 (
100 \ - Komi'thvl jonon I 15 ( Sandalhol / oil
Vl ¹ I. τ laiigol
Porridge musk Benzyl salicvlal

ht you hurry Components

Rhodinol

Nerol

Linalool

Terpineol

Phenylethyl alcohol

Terpineol

Linalyl acetate

Citronellyl acetate

Geranyl acetate

Eugenol

Citral

Phenyl ethyl acetate

Rose oxide

Guaicol

Citronellyl

Nerylacetate

Clove bud oil

Cadines

Guaien

Wreath. Resin turpentine

λ-pinene

purified myrcene

Limes

p-C'ymen

Parts by weight

270.0 90.0 30.0 30.0 12.0

5.0

1.5 15.0 10.0 30.0 15.0 20.0

8.0 30.0 93.0

3.0

1.0

2.0

1.0 12.0

1.0

5.0

2.0

1.0

687.5

Part A

30 (parts by weight of a 0.1% solution of / J-Cyckihomocitral in diallyl phthalate were added to a portion of the above mixture. This preparation hall a much livelier rose top note than the mixture without / I-Cyclolioniocitral.

part B

Were iewichtsteile a 0.1 "/" solution of / i-C'yi citral in diallyl phthalate and 15 Gewichtsieile 0.01 "/" solution of Damasceiion in Diiithylph ^"111 (a portion of the above mixture! ^ /.Ugegeben . also this preparation had a vil k'hhaflere Kosen Kopfnole and was friichligcr u "richer than when drying the mixture as ohiH ¹¹ ^ Wüiv / iigabc.

Example 25 rose essence
The basic substance was a mixture of the following:

Parts by weight

Components

Phenylethyl alcohol

Geraniol

Citronellol

«-) onon

llydroxy-citronellal

1040 390 390 130 130

2080

(A) To a sample, 208 parts of 4-damascol (2,5-dimethyl-5-phenylhexanone-4) was added.

(B) A second sample was added to 208 parts of 4-damascol and 52 parts of a 10% solution of α-cyclohomoeitral added in diallyl phthalate.

(C) 104 parts of 4-damascol and 52 parts of a 10% ß-cyclohomocitral solution were added to a third sample added in diethyl phthalate.

Table 1

(D) 208 parts of Damascol (2,5-dimethyl-5-phenylhexen-1-one-3) were added to a fourth sample.

(E) To a fifth sample, 208 parts of damascol and 52 parts / J-cyclohomocitral were added.

(F) A sixth sample was made up of 104 parts of Damascol and 52 parts of a 10% / I-cyclohomocitral solution added in diethyl phthalate.

It has been found that j3-Cyclohomocitral improves the rose character significantly when taken together with 4-Damascol / samples (B) and (C) was used.

The combination of ß-cyclohomoeitral and Damascol in samples (E) and (F) the rose character was increased considerably.

Example 26
Manufacture of soap compositions

100 g of soap flakes were mixed with an egg Seasonings according to the invention mixed homogeneously and examined. The results are in the following table compiled:

Würz / usarnmenset / ung

Warning

excellent petitgrain character with green and earthy egg

excellent woody, green, earthy aroma with a

Rose nuance

Lily of the valley character with an excellent note of flowers

pronounced and strong rose aroma
excellent rose aroma

! 'void rose aroma with earthy and green notes
Rose aroma with holy, green and earthy notes

Composition from Example 21 (Petitgrain)

/ i-Cyclohomocitral

Composition from Example 22 (lily of the valley perfume)

Composition from Example 23

(Flower perfume)
Rose scent from example 24

(Part A)
Rosendul't from example 24

(Part B)
Mixture of /K.'yclohomocilral and Damascenon:

(a) Vote ratio I: (1.1

(h) Weight ratio I: 0.2

(e) Weight ratio 1: 2

(d) Weight ratio I: I.

(e) Weight ratio 2: 1

Mixture of Damascol and /i-(.'ycloliomocilral: rose aroma with holy, green and earthy notes

(a) Weight ratio 2: 1

(b) Weight ratio I: 1

Mixture of 4-damascol and / i-cyclohoinoeitial: rose aroma with holy, green and earthy nuances (a) Weight ratio.}: I (left) Weight ratio 4: I (C) Weight ratio I: 1

Rose essence from example 25 Rose aroma with holy, green and earthy notes

(a) Sample B

(b) Sample C.
(C) sample Γ
dl) sample I

Example 27

I lerslelliing a Nelzniitlels (Reimguiigsiniltels)

K) Og Seiieiischnit / el were with Ig one of the corresponding information of the respective Würzzusan the compositions from Table I were homogeneous. mixed. The aroma of the detergent mixture

Example 28
Manufacture of a cosmetic powder

100 g of talcum powder became homogeneous with 0.25 g of one of the seasoning compositions from Table 1 mixed. The fragrance and aroma of the powder corresponded to the specifications for the respective seasoning compositions.

Example 29
Perfumed liquid detergents

Concentrated liquid wetting or cleaning agents were mixed with seasoning compositions according to Table 1 mixed homogeneously, whereby the additional amount of

The seasoning was 0.10%, 0.15% and 0.20%. The blends had the specified aroma and flavor Scent notes, with larger concentrations increasing the intensity.

Example 30

1 making a cologne
and handkerchief perfumes

The respective seasoning composition was added to cologne at a concentration of 2.5% in 85% igcm aqueous ethyl alcohol and a pocket perfume in a concentration of 20% ir 95% aqueous ethyl alcohol was added. There; The result corresponded to the information in Table 1.

Claims (1)

Patent claims: 1. Synthetic seasoning and / or flavoring for food, food spices, perfume compounds-> compositions, colognes, perfumed articles, tobacco and tobacco spices, medicinal preparations, Chewing gum consisting of (i) ZAö-Trimelhyl-l-cyelohexen-l-ylacetaldehyde in the formula acetaldehyde according to claim
draws that !, characterized by