AU730813B2

AU730813B2 - The use of substituted 5-phenyl-pentanols as aroma substances and fragrances

Info

Publication number: AU730813B2
Application number: AU87926/98A
Authority: AU
Inventors: Peter Esser; Jurgen Rabenhorst; Steffen Sonnenberg; Lutz Walther
Original assignee: Haarmann and Reimer GmbH
Current assignee: Symrise AG
Priority date: 1997-10-02
Filing date: 1998-10-02
Publication date: 2001-03-15
Anticipated expiration: 2018-10-02
Also published as: DE59806802D1; JPH11193394A; DE19743718A1; EP0908439A1; AU8792698A; EP0908439B1; ES2190023T3; JP3553390B2

Description

Our Ref: 700568 P/00/011 Regulation 3:2

AUSTRALIA

Patents Act 1990

ORIGINAL

COMPLETE SPECIFICATION STANDARD PATENT 0 00 8 0000 0 00 .00.

0 0.

.000 a a.

a Applicant(s): Haarmann Reimer GmbH D-37601 Holzminden

GERMANY

Address for Service: Invention Title: DAVIES COLLISON CAVE Patent Trade Mark Attorneys Level 10, 10 Barrack Street SYDNEY NSW 2000 The use of substituted 5-phenyl-pentanols as aroma substances and fragrances The following statement is a full description of this invention, including the best method of performing it known to me:- 5020 Y' HR 191-Foreign Countries Mn/m/NT/V10.09.1998 -1- The use of substituted 5-phenyl-pentanols as aroma substances and fragrances The present invention relates to the use of substituted 5-phenyl-1-pentanols as aroma substances and fragrances, fixatives and boosters, to novel substituted 5-phenyl-1pentanols and to a plurality of processes for the preparation thereof.

The changing trends of fashionable tastes have led not only to an increasing demand for new fragrances having interesting perfume notes, but there has also been an intensive search for new fragrances having additional properties. Of particular interest for the perfume composition are fragrances which improve the adhesion of the composition (thus act as a fixative) or increase the intensity of olfactory perception (thus function as boosters). In the case of fragrances which are functional to such a degree, it is desirable that they do not perfume too strongly and that they do not have any significant character of their own, which ensures that they can be used as widely as possible in perfume compositions.

The known fragrances of the 5-phenyl-pentanol type, namely 2 -methyl-5-phenyl-pentanol (®Rosaphen H&R) and (Phenoxanol® IFF), all have a flowery to rosy odour profile. Where adhesion is moderate, as is preferable, then there can be no discussion of fixative properties.

Besides imparting the flowery-rosy odour to a fragrance composition, they do not display any further effects, not even the booster effect mentioned above.

Surprisingly, it has been found that certain substituted 5-phenyl-l-pentanols have excellent properties as fixatives and/or boosters.

The invention provides for the use of compounds of the formula 0 I 2-C-R in which

R

R' and R 2 R' and R 2

R'-R

8 is C 1

-C

6 -alkyl, independently of one another are hydrogen, C 3

-C

8 -alkyl, C,-C 8 -alkoxy or together are methylenedioxo -O-CH 2 and independently of one another are hydrogen or C,-C 8 -alkyl 0

C.

ooo0 with the proviso that the total number of carbon atoms in substituents R' R 8 is from 2 to 8 and at least one carbon atom on the radicals R 3

-R

8 is present, as aroma substances and fragrances.

Preference is given to using those compounds I in which R' and R 2 are as defined above,

R

4

R

6 and R 7 are hydrogen and

R

3

R

5 and R 8 independently of one another are hydrogen or C 1

-C

8 -alkyl, with the proviso that the total number of carbon atoms in the substituents R' R 8 is from 3 to 8 and at least one carbon atom on the radicals R 3 -R is present.

Compounds of the formula are novel with the exception of 5-phenyl-2,4dimethyl-pentanol Amer. Chem. Soc. 1997, 119, 6496; Synlett 1997, 457), 5-(4methoxy-phenyl)-2-methyl-pentanol Org. Chem. 1972, 37, 825), 5-phenyl-2ethyl-pentanol Amer. Chem. Soc. 1934, 56, 689), 5-(4-methoxy-phenyl)-3,3- HR 191-Foreign Countries -3dimethyl-pentanol Chem. Soc., Perkin Trans. I, 1974, 394) and 5-phenyl-3,3dimethyl-pentanol (Chem. Ber. 1957, 90, 1946).

The invention thus also provides compounds of the above formula I, except for the compounds listed by name in the previous paragraph, and also perfume oils and aroma compositions containing compounds I.

The invention includes all possible isomers (enantiomers, diastereomers) and refers to all compounds which contain the novel compounds in bound, chemical or physical form and which release them under suitable conditions.

Having a property profile as weak, functional fragrances, it is surprising that the compounds differ significantly from the abovementioned fragrances pentanol, 2-methyl-5-phenyl-pentanol (Rosaphen®) and 15 (Phenoxanol®).

In individual perfume evaluation, the fragrances are generally weak fragrances having flowery to rosy aspects.They display their intensities in the perfume compositions. They provide a weak flowery base note. Above all, however, they display two further extremely notable aspects: the adhesion of a perfume composition is improved by the compounds i.e. they act as fixatives; furthermore, when the compounds are present in a perfume composition, the olfactory perception is greater, i.e. there is a booster effect.

The compounds I can be prepared according to processes known per se.

Substituted 2-alkyl-5-phenyl-l-pentanols can be prepared by reacting, for example, benzaldehyde of the formula R'R 2 PhCHO, in which the radicals R' and R 2 are as defined above and Ph is phenylene, in aldol reactions successively with acetaldehyde and with aldehydes of the formula R 7

R

8 -CH-CHO, in which R 7 and R 8 are as defined above, and subsequently hydrogenating the reaction product.

HR 191-Foreign Countries -4- Substituted 2,4-dialkyl-5-phenyl-l-pentanols can be obtained via a double aldol reaction of benzaldehydes R'R 2 PhCHO, in which the radicals R' and R 2 are as defined above and Ph is phenylene, with aldehydes of the formulae R 3

R

4

-CH

2

-CHO

and R 7

R

8 -CH-CHO, in which R 3

R

4

R

7 and R 8 are as defined above, and subsequent hydrogenation of the reaction products.

An alternative is the aldol reaction of 2

R'R

2 PhCH 2

CH(CH

3 )CHO, in which the radicals R' and R 2 are as defined above and Ph is phenylene, with aldehydes of the formula R 7

R

8 -CH-CHO, in which R7 and R 8 are as defined above, and subsequent hydrogenation of the reaction product.

2-Alkyl-5-phenyl-l-pentanols are obtained by reacting cinnamic aldehyde of the *o.

formula R

R

3

CH=C-CHO

R2 in which

R

3 are as defined above, with aldehydes of the formula R 7

R

8 -CH-CHO, in which R 7 and R 8 are as defined above, in an aldol reaction, and subsequently hydrogenating the reaction product.

The aldol condensation reactions can be carried out in a manner known per se, e.g.

Organikum [Organic Chemistry], 19th edition, Barth Verlagsgesellschaft, Leipzig 1993, pages 467 et seq., Org. React. 1968, 16, 1-438 or Methoden der Organischen Chemie [Methods of Organic Chemistry] (Houben-Weyl), Vol. 21 b, Thieme Verlag, Stuttgart 1995, 1603 et seq. Preferred solvents are alcohols, such as methanol or HR 191-Foreign Countries ethanol, in which the basic catalyst, preferably an alkali metal hydroxide, for example sodium hydroxide and/or potassium hydroxide, is dissolved.

The reaction temperature is usually from -20 to 50, preferably from 0 to 30 0 C. At this temperature, the two aldehydes are metered in. The molar ratio of the higher molecular weight aldehyde to the lower molecular weight aldehyde is usually from 1 to 3, preferably from 1.1 to 2. The aldehydes can be added undiluted or dissolved in the solvent, such as in alcohols or in water.

If one of the two aldehyde components is acetaldehyde, it may be advantageous to add the acetaldehyde dissolved in solvents such as alcohols or water, preferably in S. water, to the other aldehyde components together with the alkaline solution. The ~secondary reaction may last from I to 48 hours, preferably from 3 to 24 hours.

The reaction solution can be worked up by firstly neutralizing it, using acetic acid, ***for example. The solvent can then be distilled off, if necessary under reduced Spressure.

e• The distillation residue can be taken up in water and an organic solvent. The organic ooeo• solvents used may be aromatic hydrocarbons, such as toluene, or ethers or esters. The organic phase can then be distilled. If the reaction product is precipitated from the reaction solution, then, after the reaction mixture has been neutralized, the reaction product can be filtered off and purified by recrystallization.

The unsaturated aldehyde obtained after one or after two aldol condensation reactions can be hydrogenated without a diluent or in an alcoholic solvent, for example methanol, ethanol or isopropanol. The hydrogenation catalysts used may be standard commercial catalysts such as Raney nickel, palladium/carbon or platinum/carbon.

Pressures of, in general, from 1 to 30 bar, preferably from 5 to 20 bar, in particular from 8 to 15 bar, and hydrogenation temperatures of from 20 to 120 0 C, preferably from 40 to 100 0 C, may be chosen.

HR 191-Foreign Countries -6which have different substituents on the phenyl ring can also be obtained analogously to known reactions by Friedel-Crafts alkylation of phenyl-1 -pentanols.

Prior to the alkylation reaction, the alcohol group is advantageously protected, e.g. by esterification to the acetate. For this purpose, the phenylpentanol can be mixed together with acetanhydride (usual molar ratio from 1 to 2, preferably from 1 to 1.3).

At a reaction temperature of, usually, from 80 to 120 0 C, preferably from 90 to 110 0 C, and reduced pressure, acetic acid distils off first.

The phenylpentyl ester can be alkylated by mixing it with an alkane, for example hexane or heptane, an aromatic hydrocarbon, for example toluene or xylene, or a cycloalkane, for example cyclohexane or methylcyclohexane.

Suitable catalysts are Lewis acids, for example aluminium(III) chloride, titanium tetrachloride or iron(III) chloride.

At a temperature of from 40 to 100 0 C, preferably from 40 to 60 0 C, the olefin is added. The molar ratio of phenylpentyl ester: olefin is usually from 1 to 3, preferably S. from 1.1 to 2.

The alkylphenylpentyl ester undergoes transesterification to give the desired alkylphenylpentanol. For the transesterification, alcohols such as methanol or ethanol are suitable. They are used in a significant molar excess. The molar ratio of alkylphenylpentyl ester:alcohol is usually from 2 to 10, preferably from 3 to Suitable transesterification catalysts are bases, for example alkali metal alkoxides, such as sodium methoxide or sodium ethoxide.

HR 191-Foreign Countries -7- The transesterification equilibrium can be shifted to the desired side by distilling off ester.

which have different substituents on the phenyl ring can be obtained via Prins reaction and hydrogenation stages. In the Prins reaction, aromatic aldehydes R'R 2 PhCHO, in which the radicals R' and R 2 are as defined above and Ph is phenylene, and 3-methyl-3-butene-1-ol are reacted together.

The aromatic aldehyde and 3-methyl-3-buten-l-ol are preferably used in equimolar quantities. Suitable solvents are aromatic hydrocarbons, for example toluene or xylene, alkanes, for example hexane or heptane, cycloalkanes, for example cyclohexane or methylcyclohexane, or ethers or esters.

The reaction can be acid-catalyzed. Suitable acidic catalysts are aromatic sulphonic acids and alkanesulphonic acids, for example p-toluenesulphonic acid or methanesulphonic acid, mineral acids, or their acidic salts, for example sulphuric acid or potassium hydrogensulphate, and acidic ion exchangers, as are available, for example, under the trade names ®Lewatit or ®Amberlite. Acidic ion exchangers are S. particularly preferred acidic catalysts.

By boiling at the water separator and removing the water reaction, it is possible to shift the reaction equilibrium to the desired products.

The product from the Prins reaction can be converted into the desired phenylpentanol by hydrogenation. The hydrogenation catalysts chosen may be the abovementioned hydrogenation catalysts at hydrogenation pressures of from 1 to 30 bar, preferably from 5 to 20 bar, in particular from 8 to 12 bar, at hydrogenation temperatures of, in general, from 20 to 120 0 C, preferably from 40 to 100 0

C.

HR 191 -Foreign Countries Table 1: Odour of the compounds Only the aspects extending beyond rosy and flowery are given.

Comp. R' R' R' R 4 R' R 6 R' R' Odour No.

4-i-Pr 4-t-Bu 4-MeO H H Me H HMe H HMe 4 3,4- Methylenedioxo 5 4-i-Pr 6 4-t-Bu 7 4-MeO 8 3,4- Methylenedioxo 9 4-i-Pr 4-t-Bu I1I 4-MeO 12 3,4- Methylenedioxo 13 H H H H H H HMe slightly fruity towards p-cresol slightly aniseed-sweet, like heliotropin dimethyl resorcinate, fatty alcohol Weak slightly fatty, perillaldehyde H HMe H H Me H H Me H H Me H H H Me H H H Mimosa H H H Me HH H Weak H H H Me H H H Hydroxycinnamyl alcohol H H H Me H HH p-cresol H H H H H H Et Hydroxycinnamyl alcohol, styrex H H H H H H Pr reseda ketone H H H H H Hi-Pr Fruity Me =methyl, MeO methoxy, Et ethyl, Pr n-propyl, i-Pr =isopropyl, t-Bu tert-butyl 14 H-

H

Abbreviations: HR 191-Foreign Countries -9- Fragrance compositions containing the novel compounds display an altogether more complex, perfume effect. A significant increase in perfume adhesion can generally be established. Moreover, a booster effect is evident, i.e. the olfactory perception is significantly increased by additives of compounds compared with the same fragrances or fragrance compositions without compounds The described influences of compounds on fragment compositions become apparent particularly when comparing the change in odour with time in practice.

Compounds I to be used according to the invention can be readily combined with •other fragrances in varying quantity ratios to give new types of interesting fragrance S0:" compositions, in which case the amount is from 0.1 to 60% by weight, preferably from 0.5 to 40% by weight, based on the overall composition.

As well as being used in fine perfumes, compositions of this type can also be used •for perfuming cosmetics such as creams, lotions, aerosols, toilet soaps, deodorants, household products, such as detergents and cleaning products, fabric conditioners, disinfectants and textile treatment agents, in which case the amount of fragrance composition is from 0.1 to 40% by weight, preferably from 0.5 to 20% by weight, based on the overall product.

0Suitable carriers for these fragrance chemicals are alcohols (methanol, ethanol, npropanol, iso-propanol and butanol) and oils known in the art. It is of course possible to combine the compounds of invention with other common fragrance chemicals, such as animal perfumes such as musk oil, civet, castreum, ambergris, plant perfumes such as sandalwood oil, neroli oil, bergramot oil, lemon oil, lavender oil, sage oil, rosemary oil, peppermint oil, eucalyptus oil, verbena oil, citronella oil, grapefruit oil, salvia oil, clove oil, chamomille oil, costus oil, labdanum oil, broom extract, carrot seed extract, jasmine extract, mimosa extract, narcissus extract, olibanum extract, rose extract and the like; and chemical substances such as acetophenone, dimethylindane derivatives, naphthalene derivatives, allyl caprate, oc-amylcinnamic HR 191-Foreign Countries aldehyde, anethole, anisaldehyde, benzyl acetate, benzyl alcohol, benzyl propionate, borneol, cinnamyl acetate, cinnamyl alcohol, citral citronellal, cumin aldehyde, cyclamen aldehyde, decanol, ethyl butyrate, ethyl caprate, ethyl cinnamate, ethyl vanillin, eugenol, geraniol, hexenol, oc-hexylcinnamic aldehyde, hydroxycitronellal, indole, iso-amyl acetate, iso-amyl iso-valerate, iso-eugenol, linalol, linalyl acetate, pmethylacetophenone, methyl anthranilate, methyl dihydrojasmonate, methyl eugenol, methyl-p-naphthol ketone, methylphenylcarbinyl acetate, musk ketol, musk xylol, ynanolactone, phenylacetoaldehydodimnethyl acetate, P-phenylethyl alcohol, 3,3,5trimethylcyclohexanol, y-undecalactone, undecenal, vanillin and the like. The perfumes may be used singly or in combination.

:The percentages in the examples below are in each case by weight.

gee• HR 191-Foreign Countries -ll- -11- Examples Example 1: 2-Methyl-5-(4-isopropylphenyl)-pentanol (1) 3 4 -Isopropylphenyl)-prop-2-en- I-one A solution comprising 1000 ml of methanol, 4 g of sodium hydroxide and 148 g of cuminaldehyde is cooled to 4 0 C. Over the course of one hour, an aqueous acetaldehyde solution (70.6 g in 100 g of water) is added, during which the temperature rises to 10 0 C. The mixture is stirred for a further hour at 10 0 C and then overnight without further cooling.

0 0 In the morning, the mixture is neutralized using 6 g of acetic acid, and the methanol 0 is stripped off in a water-pump vacuum. It is taken up in 6 g of soda, dissolved in 200 ml of water, and 600 ml of toluene. Following phase separation, the toluene is stripped off.

The batch is repeated three times. On average, the crude GCs have 35% of starting material and 31% of product. The combined four batches are distilled over a 30 cm packed column (V4A helices). In the main fraction, 161 g of 3-(4-isopropylphenyl)prop-2-en-l-one are produced at a still temperature of 160-190°C and a head temperature of 102-117°C 0.6 mbar.

4 -isopropylphenyl)-penta-2,4-dien- -one A solution of 162 g of p-isopropyl cinnamic aldehyde and 62 g of propionaldehyde in 200 ml of methanol is added to a solution of 20 g of sodium hydroxide in 500 ml of methanol thermostatted to 20 0 C. The batch is further stirred overnight.

After 31 ml of acetic acid have been added to the mixture, the methanol is stripped off in a water-pump vacuum. The residue is taken up in a solution of 6 g of soda in HR 191-Foreign Countries -12- 200 ml of water and 300 ml of toluene. The organic phase is distilled. In the main fraction, 107 g of 2-methyl-5-( 4 -isopropyl-phenyl)-penta-2,4-dien- -one are produced at a still temperature of 180-240°C and a head temperature of 127- 140 0 C/0.2 bar.

2 -Methyl-5-(4-isopropylphenyl)-pentanol (1) The 107 g of 2 -methyl-5-(4-isopropylphenyl)-penta-2,4-dien-l-one are made up to 500 ml using isopropanol and hydrogenated with 5% Raney nickel at a hydrogen pressure of 10 bar and a maximum temperature of 100°C.

After the Raney nickel has been filtered off, the mixture is distilled over a 30 cm packed column to give 71.3 g of 2-methyl-5-(4-isopropylphenyl)-pentanol 15 Example 2: 2,4-Dimethyl-5-(4-isopropylphenyl)-pentanol 2 4 -Dimethyl-5-(4-isopropylphenyl)-pent-2-en-1 -one A mixture of 380 g of cyclamen aldehyde and 133.4 g of propionaldehyde at 20 0

C

0 are added to 500 ml of methanol and 20 g of sodium hydroxide in a double-walled vessel over the course of 2 hours. The mixture is then stirred overnight.

The mixture is neutralized by adding 30 g of acetic acid, and the methanol is stripped off in a water-pump vacuum. The remaining material is taken up in a solution of 6 g of soda in 200 ml of water and 300 ml of toluene, a spatula tip of Jonol is added to the mixture, and the organic phase is evaporated in a water-pump vacuum on a rotary evaporator. The mixture is then fractionally distilled twice over a 30 cm packed column. After the second distillation, 102 g of the 2,4-dimethyl-5-(4-isopropylphenyl)-pent-2-en-l-one are obtained at a still temperature of up to 200 0 C and a head temperature of 122-126 0 C/0.5 mbar.

HR 191-Foreign Countries 13- 2 ,4-Dimethyl-5-(4-isopropylphenyl)-pentanol 102 g of 2 4 -dimethyl-5-(4-isopropylphenyl)-pent-2-en-1-one are made up to 500 ml using methanol and hydrogenated with 5% Raney nickel at a hydrogen pressure of 10 bar and a maximum temperature of 100 0

C.

After the Raney nickel has been filtered off, the mixture is distilled over a 30 cm packed column (120 0 C; 0.62 mbar) to give 58.5 g of 2 4 -dimethyl-5-(4-isopropylphenyl)-pentanol Example 3: 3-Methyl-5-(4-methoxyphenyl)-pentanol (11) 6O

S.

Reaction of anisaldehyde with 3-methylbutenol A batch of 272.4 g of anisaldehyde, 175.3 g of 3-methylbutenol, 1000 ml of toluene and 10 g of Lewatit SPC® 118 Bayer (very acidic) is refluxed throughout the day in a 2 1 three-necked flask on a water separator. 35 g of water are eliminated. After the ion exchanger has been filtered off, the mixture is evaporated in a water-pump vacuum on a rotary evaporator. A spatula tip of Jonol and 1 g of sodium hydrogencarbonate are added and the mixture is then distilled over a 50 cm packed column. After the starting material has been removed, 110 g of the two isomeric products are obtained ooat a still temperature of 160°C to 170C and at a head temperature of 98 0 C to 108 0 C 0.16 mbar.

3-Methyl-5-(4-methoxyphenyl)-pentanol (11) 110 g of the two isomeric products from the preliminary stage are made up to 500 ml with methanol and hydrogenated with 1% Pd/C at a hydrogen pressure of 7 bar and a maximum temperature of 100 0

C.

HR 191-Foreign Countries -14- After the Pd/C has been filtered off, the mixture is distilled over a 30 cm packed column to give 55.4 g of 3-methyl-5-(4-methoxyphenyl)-pentanol (11) at a head temperature of 113 0 C 0.065 mbar.

Example 4: 2-Ethyl-5-phenyl-pentanol (13) 2-Ethyl-5-phenyl-penta-2,4-dien-1-one A mixture of 264 g of cinnamic aldehyde and 165.6 g of butanal are added dropwise to 500 ml of methanol and 20 g of sodium hydroxide, contained in a reaction vessel thermostatted to 20 0 C, under a nitrogen atmosphere and with stirring in the course of 4 hours. The batch is further stirred overnight.

4 The mixture is then neutralized using 30 g of acetic acid and the methanol is then 15 stripped off in a water-pump vacuum. The remaining material is taken up in 300 ml of toluene and washed with a solution of 6 g of soda in 200 ml of water. The organic phase is evaporated in a water-pump vacuum on a rotary evaporator. The mixture is ~distilled in an oil-pump vacuum. The main fraction contains different isomeric products, has a boiling point of 111°C 0.18 mbar and weighs 254 g.

2-Ethyl-5-phenyl-pentanol (13) 254 g of 2-ethyl-5-phenyl-penta-2,4-dien-l-one are made up to 500 ml using methanol and hydrogenated with 5% Raney nickel at a hydrogen pressure of 10 bar and a maximum temperature of 100 0 C. After the Raney nickel has been filtered off, the mixture is distilled over a 30 cm packed column (91 0 C, 0.038 mbar) to give 146.9 g of 2-ethyl-5-phenyl-pentanol (13).

HR 191-Foreign Countries Example 5: 5-(4-tert-butylphenyl)-2-methyl-l-pentanol (2) 2-Methyl-5-phenyl-1 -pentenyl acetate 445 g of 2-methyl-5-phenyl-pentanol and 280 g of acetic anhydride are heated to a still temperature of 100'C at a pressure of 200 mbar. At this temperature, the acetic acid starts to be eliminated (exothermic, temperature increase to 105 0 Acetic acid is then distilled off. 530 g of 2-methyl-5-phenyl-l-pentyl acetate are obtained as the main fraction (still temperature 146-150 0 C, head temperaturel09-l12 0 C 0.6 mbar).

5-(4-tert-Butylphenyl)-2-methyl-1 -pentyl acetate 420 g of iron(III) chloride are added in portions to a 530 g of pentyl acetate in 1500 g of cyclohexane over the course of 30 min (slightly exothermic: temperature increase from 20 0 C to 35 0 The mixture is heated to 50 0 C in a water bath, and 83 1 of isobutene are introduced at this temperature over the course of min. The secondary reaction takes place for 30 min at 50 0 C. The warm batch is poured onto a mixture of 750 g of hydrochloric acid and 1750 g of ice. The organic phase is washed firstly with 500 g of water and then with 490 g of water; 10 g of 20 technical-grade NaOH (50% solution) is then added thereto. The organic phase is distilled over a 30 cm packed column up to a still temperature of 60°C, and a head temperature of 51-55 0 C 500-100 mbar. The residue, distilled at 220 0 C 1 mbar jacket temperature over a thin-film evaporator, produces 595 g of 5-(4-tert-butylphenyl)-2-methyl-1-pentyl acetate as distillate.

5-(4-tert-Butylphenyl)-2-methyl- -pentanol (2) A mixture of 595 g of 5-(4-tert-butylphenyl)-2-methyl-l-pentyl acetate, 200 g of methanol and 3.5 g of sodium methoxide powder is slowly heated to 65 0 C at atmospheric pressure. At this temperature, the transesterification starts (exothermic, temperature increase to 75C, vigorous boiling), and the methyl acetate/methanol HR 19 1-Foreign Countries -16azeotrope distils off. After the methyl acetate/methanol initial fractions have been removed, a main fraction of 430 g is obtained at a still temperature of 180-200 0 C and a head temperature of 13 1 0 C/O. 6 mbar. According to GC analysis, the product has, in addition to 89% of 5-(3-tert-butylphenyl)-2-methyl-1-pentanol 4.3% of 5-(3-tertbutylphenyl)-2-methyl-l1-pentanol and 1.1% of 5 ,4-di-tert-butylphenyl)-2-methyl- 1 -pentanol.

HR 191-Foreign Countries -17- Application Example 1 5-(4-tert-Butylphenyl)-2-methyl-l-pentanol (Compound 2) is incorporated into a floral fragrance composition. The numbers in front of the individual components are their proportion of the composition given in parts by weight:

S.

1 85 120 30 30 15 15 40 5 1 4 30 20 20 20 7 100 25 2 10 7 Bergamot oil, colourless H&R Methyl anthranilate Datilat H&R Lilial® Givaudan/Roure Lyral® IFF Mugetanol® H&R Linalool Freesiol® H&R Terpineol, alpha Geranium oil, African Rosenoxide L Phenylethyl phenylacetate Phenylethyl alcohol Citronellol Rosaphen® H&R Geranyl acetate Benzyl acetate Methyldihydrojasmonate Ylang Ylang oil II Hexenyl salicylate cis-3 Benzyl salicylate Beta ionone Givaudan/Roure Boronal® H&R Iraldein, Gamma H&R Eugenol HR 191-Foreign Countries 18- 3 3 20 4 1 10 10 40 10 2 50 15 100 Isoeugenol, cryst.

Heliotropin Vanillin Benzyl cinnamate Acetylcedrene Boisanol® H&R Palisandal® H&R Sandolen® H&R Ambroxide® H&R CPD Cyclopentadecanolide Supra® H&R Galaxolid 50 IFF Ambrettia® H&R Indoflor Cryst." H&R Magnolan® H&R 5-(4-tert-Butylphenyl)-2-methyl-l-pentanol (Compound 2) A floral fragrance composition of this type is suitable, for example, for alcoholic deodorant sprays. Containing this novel Compound 2, the fragrance composition is significantly more flowery and fruity. The overall impression is more perfumed and 20 more complex. The adherence of the fresh flowery notes is prolonged.

When a deodorant spray of this type is used on the skin, the effect of adding Compound 2 is evident to a significant degree in the odiferous change over time. The top note is less diffuse and significantly more flowery and fruity (booster effect). The middle note is more flowery, more perfumed and more complex (booster, fixative effect). The base note shows a longer adhesion of the fresh and flowery notes, it is altogether softer (fixative effect). It is also noteworthy that the addition of compound in perfume oil also significantly reduces and prevents for longer the formation of the unpleasant smell of sweat.

HR 191-Foreign Countries 19- Application Example 2 5-(4-Isopropyl-phenyl)-2-methyl-l-pentanol (Compound 1) is incorporated into a fruity fragrance composition. The numbers in front of the individual components are their proportion of the composition, given in parts by weight: 4 4 60 2 10 45 20 100 10 30 10 200 50 Aldehyde-C 11 undecylenic Aldehyde-C12 lauric Dihydromyrcenol Terpinyl acetate Mandaril® H&R Lavandin oil, gross Lilial® Givaudan/Roure Mugetanol® H&R Linalool Terpineol Rose H&R Rosenoxide L 10 DPG Phenylethyl phenylacetate Benzyl acetate alpha-Hexylcinnamic aldehyde Ylang, artificial H&R Isoraldein 70® Givaudan/Roure Isoeugenol methyl ether Anisaldehyde Coumarin Oryclon® H&R Herbaflorat® H&R Habanolid 50 Firmenich Tonalid® PFW Dipropylene glycol HR 191-Foreign Countries Frutinate® H&R 100 5-(4-Isopropylphenyl)-2-methyl- 1-pentanol (Compound 1) A fruity fragrance composition of this type is suitable, for example, for soaps. 5-(4- Isopropyl-phenyl)-2-methyl-l-pentanol (Compound 1) gives this fruity composition more of a floral body in the soap bar. When the soap solution has been applied to the skin, a softer flowery note is perceptible in the case of the composition containing 4 -isopropylphenyl)-2-methyl-l-pentanol. Furthermore, the overall fragrance development is delayed, resulting in a significantly longer adhesion.

Application Example 3 5-(4-tert-Butylphenyl)-3-methyl-l-pentanol (Compound 10) is incorporated into a citrus fragrance composition. The numbers in front of the individual components are their proportion of the composition, given in parts by weight: S S

S

*S*S

2 2 1 235 2 1 240 1 5 2 Cl 1 aldehyde 10% DPG Isoananate® H&R Vertocitral 10%® H&R Floropal® H&R Hexenyl acetate Bergamot oil, colourless H&R Galbanum Synthessence 10% H&R Indoflor cryst. 10%® H&R Dihydromyrcenol Tamarinia® H&R Oxania Base® Firmenich Lavender oil Artemisian oil, Morocco Estragol Heliofolal® H&R HR 191-Foreign Countries -21 20 1 5 10 3 15 10 15 1 1 5 20 85 100 Lyral® IFF Mugetanol® H&R Tetrahydrolinalool Terpineol Geranium Boubon Synthessence® H&R Phenylethyl alcohol Citronellol Geraniol Rosaphen® H&R Damascon, alpha Benzyl acetate Methyldihydroj asmonate alpha-hexylcinnamic aldehyde Hexenyl salicylate, cis-3 Hexyl salicylate Isoraldein 70 Givaudan Roure Heliotropin Vanillin Oryclon special® H&R Boisanol® H&R Palisanda®l H&R Sandolen® H&R Globalid 50 DPG® H&R Cumarinia® H&R Claritone® H&R 5-(4-tert-Butylphenyl)-3-methyl-l-pentanol (Compound A fragrant composition of this type having a citric note is suitable, for example, for shampoos. The use of 5-(4-tert-butylphenyl)-3-methyl-l-pentanol (Compound achieves harmonization of the fresh and transparent top note with the rosy middle HR 191-Foreign Countries -22note. Moreover, an increase in the adherence of the overall composition to the hair is also perceptible.

Application Example 4 5-(4-tert-Butylphenyl)-2,4-dimethyl-l-pentanol (Compound 6) is incorporated into a citrus fragrance composition. The numbers in front of the individual components are their proportion of the composition, given in parts by weight: S.

S

5.5.

S.

10 3 5 8 8 15 50 15 15 8 5 1 3 10 2 3 80 Precyclemon B® IFF Vertocitral® H&R Allylamyl glycolate® IFF Isoananate® H&R Bergamot oil, colourless H&R Dihydromyrcenol Grapefruit oil H&R Lavender oil, gross Eucalyptus oil Artemisian oil, Morocco Thyme Vitessence H&R Basil Vitessence H&R Fir Balsam Hyperessence, colourless Jasmaprunate® H&R Lilial® Givaudan Roure Mugetanol® H&R Mimose Vitessence H&R Nigritella Vitessence H&R Damascenon® Firmenich Damascon delta Firmenich Methyldihydrojasmonate alpha-Hexylcinnamic aldehyde HR 191-Foreign Countries -23- 3 50 10 40 30 3 15 2 80 107 100 Hexenyl salicylate, cis-3 Hexyl salicylate Isoraldeine 70® Givaudan Roure Vanillin Agrumex HC® H&R Herbaflorat® H&R Cyclaprop® IFF Cedryl ketone Boisanol® H&R Patchouli oil, decolourized H&R Sandel 80® H&R Sandolen® H&R Evernyl® Givaudan Roure Ambroxan® Henkel Ambrettolid® H&R CPD Cyclopentadecanolide supra® H&R Globalid 50%® DEP Claritone®H&R 5-(4-tert-Butylphenyl)-2,4-dimethyl-1-pentanol (Compound 6)

S

*S

A fragrance composition of this type having a citrus note is suitable, for example, for fabric softeners. The top note of the fresh and light composition is further raised by adding 5-(4-tert-butylphenyl)-2,4-dimethyl-l-pentanol (Compound Moreover, so that further harmonization is achieved compared with the original composition.

When the perfume oil is used in a fabric softener on cotton, an increased adhesion overall as a result of the addition of 5-(4-tert-butyl-phenyl)-2,4-dimethyl-l-pentanol (Compound 6) is perceptible.

P:\WPDOCS\PAnCOMPRISE. 2110/98 -23a- Throughout this specification and the claims which follow, unless the context requires otherwise, the word "comprise", or variations such as "comprises" or "comprising", will be understood to imply the inclusion of a stated integer or step or group of integers or steps but not the exclusion of any other integer or step or group of integers or steps.

o4 4.

Claims

1. Use of compounds of the formula 0 000 @0 0 in which R R' and R 2 R' and R 2 R'-R' C is C 1 -C 6 -alkyl, independently of one another are hydrogen, C 3 -C,-alkyl, alkoxy or together are methylenedioxo -O-CH 2 and independently of one another are hydrogen or C,-Cs-alkyl with the proviso that the total number of carbon atoms in substituents R' R 8 is from 2 to 8 and at least one carbon atom on the radicals R-R 8 is present, as aroma substances and fragrances.

2. Use according to Claim 1, where 4*00/ 0 @00. S R' and R 2 R 4 R 6 and R 7 R 3 R' and R 8 are as defined in Claim 1, are hydrogen and independently of one another are hydrogen or C,-C 8 -alkyl, with the proviso that the total number of carbon atoms in the substituents R' R 8 is from 3 to 8 and at least one carbon atom on the radicals R-R 8 is present.

3. Use according to Claim 1, where HR 19 1-Foreign Countries 25 R1 R 2 R' and R' R 8 is C 3 -C 8 -alkyl or C 1 -C 8 -alkoxy, is hydrogen or together are methylenedioxo -O-CH 2 are hydrogen and is methyl.

4. Use according to Claim 1, where e R' and R 2 R 4 -R' R 3 and R 8 is C 3 -C 8 -alkyl or C 1 -C 8 -alkoxy, is hydrogen or together are methylenedioxo -O-CH 2 are hydrogen and are methyl.

5. Use according to Claim 1, where R1 R' andR 2 R3- R 4 and R 5 is C 3 -C 8 -alkyl or C 1 -C 8 -alkoxy, is hydrogen or together are methylenedioxo -O-CH 2 are hydrogen and is methyl.

6. Use according to Claims I to 5 as fixatives and/or boosters.

7. Compounds of the formula according to Claim 1, except for -phenyl-2,4-dimethyl-pentanol, 5-(4-methoxy-phenyl)-2-methyl-pentanol, 5-phenyl-2-ethyl-pentanol, -26- 5-(4-methoxy-phenyl)-3,3-dimethyl-pentanol and 5-phenyl-3,3-dimethyl-pentanol.

8. Compounds according to Claim 7, where R' and R 2 R 4 R 6 and R 7 R 3 R 5 and R 8 are as defined in Claim 1, are hydrogen and independently of one another are hydrogen or C,-C 8 -alkyl, with the proviso that the total number of carbon atoms in the substituents R' R 8 is from 3 to 8 and at least one carbon atom on the radicals R 3 -R 8 is present.

9. Process for the preparation of the compounds according to Claim 7 or 8 by 15 S. S S. So S Se a) reaction of 5-phenyl-1 -pentanol esters of the formula S *554 .55 20 0 S **S S 555 SOS in which R R' and R 2 R'-R 8 is C,-C 6 -alkyl, are hydrogen and are as defined in Claim 1, with C 3 -C 8 -olefins in the presence of Lewis acid and subsequent hydrolysis or HR 191-Foreign Countries -27- b) reaction of benzaldehydes R' R 2 PhCHO, in which the radicals R' and R 2 are as defined in Claim 1 and Ph is phenylene, in aldol reactions successively with acetaldehyde and an aldehyde of the formula R 7 R 8 CH-CHO in which R 7 and R 8 are as defined in Claim 1, and subsequent hydrogenation of the resulting reaction product, or c) reaction of benzaldehydes R'R 2 PhCHO, in which the radicals R' and R 2 are as defined in Claim 1 and Ph is phenylene, successively with one equivalent of each of the aldehydes of the formulae 9 4* *r a R 3 R 4 CH-CHO and R 7 R 8 CH-CHO in which R 3 R 4 R 7 and R 8 are as defined in Claim 1, and subsequent hydrogenation of the resulting reaction product, or d) reaction of 2-methyl-5-phenyl- -propanals R'R 2 PhCH 2 CH(CH 3 )CHO, in which the radicals R' and R 2 are as defined in Claim 1 and Ph is phenylene, with aldehydes of the formula R 7 R 8 CH-CHO in which R 7 and R 8 are defined in Claim 1, and subsequent hydrogenation of the resulting reaction product, or e) reaction of cinnamic aldehydes of the formula HR 191-Foreign Countries -28- S-CH=C-CHO R2)D in which R 3 are as defined in Claim 1, with aldehydes of the formula R 7 R-CH-CHO in which R 7 and R 8 are as defined in Claim 1, and subsequent hydrogenation of the resulting reaction product; or f) reaction of benzaldehydes R'R 2 PhCHO, in which the radicals R' and R 2 are as defined in Claim 1 and Ph is phenylene, in a Prins reaction with 3-methyl-3-buten-l-ol and subsequent hydrogenation of the resulting reaction product.

Perfume oils or aroma compositions containing compounds I according to Claim 1.

11. Compounds of the formula uses of the same methods for their manufacure or compositions or methods of use involving/containing them, substantially as hereinbefore descried with reference to the Examples. DATED this 2nd day of October 1998 HAARMANN REIMER GMBH By Its Patent Attorneys DAVIES COLISON CAVE