DE2431039A1 - USE OF 2,6,10-TRIMETHYL-10HYDROXYDODECA-2,6,11-TRIEN-1-AL AS A FRAGRANCE - Google Patents

Description

Paluitai, v.ält · ■

Dipl.-I.ig. ?. Wi.th case 1210

Dr. V. Schniied-Kowarzik

Dipl.-Ing. G. Dannenberg 2 & 3 1 0 3 9

Dr. P. Weinhold, Dr. D. Gudel 6 Frankfurt / M., Gr. Eschenheimer sir. 39

PIRMENICH SA in Geneva

Use of 2,6,10-trimethyl-10-hydroxydodeca-2,6 _> ll-triene-1-al as a fragrance

The present invention relates to
Use of 2,6,10-trimethyl-10-hydroxy-dodeca-2,6,11-trien-1-al as a fragrance, to fragrance compositions and perfumed products containing this substance and to a process for the production of 2,6,10 -Trimethyl-10-hydroxy-dodeca-2,6,11-trien-1-al. »*

2,6,10-trimethyl-10-hydroxy-dodeca-2,6,11-triene-1-al the formula

CH-. CH, CH,
I 3 I 3 ι 3
CH ₂ = CH-C-CH ₂ -CH ₂ -CH = C-CH ₂ -Ch ₂ -CH = C-CHO · I

OH. ·

is a well-known connection (see German DOS 2'143'992J, which as an intermediate product for the synthesis of a-Sinensal and ß-Sinensal is used. The two sinensals are components

the natural tangerine aroma. The aldehyde I is also known under the name "Hydroxysinensal ¹¹ ".

Since the "structure of the Hydpoxysinensas that of the is very similar to both Sinensale, it could be expected that Hydroxysinensal would also have a similar odor, i.e. would develop a tangerine-like odor, or at least a tangerine-like odor, as in the one above mentioned DOS is mentioned. However, this assumption has not been confirmed. Namely, it was found that the odor of the hydroxy sinensals is completely different from that of the Sinensale. The smell of the hydroxysin salmon is not fruity, it is floral and reminiscent of the perfume of the lily of the valley. This odor is also very persistent. There is also the smell of the aldehyde I completely free of the citrus note that characterizes the Sinensale. Hydroxysinensal is already a finished product as such Perfume. It can be used as a base for the production of fragrance compositions or as an odor-modifying additive for perfume compositions can be used and enables very interesting flowery odor effects to be achieved.

The invention relates to a method for improving, amplifying or otherwise changing the odor properties of fragrance compositions, perfumed products and natural or synthetic essential oils through use of 2,6,10-trimethyl-10-hydroxydodeca-2,6, ll-triene-l-al as a fragrance component or odor-changing additive.

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The invention also relates to fragrance _{compositions 3} perfumed products and natural or synthetic essential oils ₉ which are characterized by a content of 2,6,10-trimethyl-10-hydroxy-dodeca-2,6, ll * -trien-l-al are.

Finally, the invention relates to a process for the preparation of 2, öjlO-trimethyl-10-hydroxy-dodeca ^ jöjlltrien-l-al, which is characterized in that nerolidoi (TI) N-bromosuccinimide is allowed to act in order to convert 2-methyl- 2-vinyl-5- (l _> 5 ~ dimethyl-l-bromo-hex-Jj-en-l-yl) -tetrahydrofuran (III), the latter converted into its mono-ozonide and the ozonide to 2-methyl -2-vinyl-5- (l-methyl-l-bromo-3-formylprop-1-yl) -tetrahydrofuran (IV) reduced, the aldehyde (IV) acetalized, on the acetal obtained (V) first a reducing metal in a practically anhydrous medium and then water to act, the resulting 4,8-dimethyl-8-hydroxydeca-4,9-dien-l-al-acetal (VI) hydrolyzed to 1,8-dimethyl-8-hydroxy- deca- ¹ }, 9-dien-l-al (VII), and subjecting the latter to a Wittig reaction with 1-formyl-ethylidene-triphenylphosphorane to give 2,6,10-trimethyl-10-hydroxy-dodeca- 2,6, ll-trien-1-al.

The term used in this description

"Perfumed product" includes, for example, cosmetic products, soaps, cleaning and laundry detergents, and the like.

Hydroxysinensal can be used as such on its own, i.e. without adding other fragrances, as a perfume,

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preferably in diluted form. The ones commonly used in perfumery Diluents or solvents can be used for this purpose, e.g. ethyl alcohol or phthalic acid diethyl ester, The Hydroxysinensal can be used to perfume soaps, cosmetic products, detergents and cleaning agents and the like will.

If Hydroxysinensal is used as a fragrance component together with other fragrances in fragrance compositions, its concentration can be in a wide range, for example between 2 and 20 %, based on the total weight of the perfume composition. The concentration of Hydroxyuinensal can, however, exceed 20% and, for example, 50 % or even more, depending on the odor effect to be achieved.

The inventive method for the production of Hydroxysinensal can be illustrated by the following reaction scheme will:

f ^H 3 f ^H 3 f ^H 3

CH ₂ = CH-C-CH ₂ -CH ₂ Ch = C-CH ₂ -CH ₂ -CH = C-CH ₃ II

OH

N-bromosuccinimide

III 409884/1460

-w-

N-bromosuccinimide

CH,

I 3 ι D \ ι

CH "= CH-C-CH" -CH "-CH-C-CH- ₂ -CH -CH = C-CH ₃

-C-CH ₂ -CH ₂ -C

III

0- 'Br

1) ozonation

2) reduction

-C-CH

IV

Acetalization

Q-R

1) reducing metal

2) H ₂ O

CH

CH ₃ OR

f ^H 3 CH ₃

CH ₂ = CH-C-CH ₂ -CH ₂ -CH = C-CH ₂ -CH ₂ -CHj OH O- ft

VI

? ^H 3

hydrolysis

CH ₂ = CH-C-CH ₂ -Ch ₂ -CH = C-CH ₂ -CH ₂ -CHO OH

VII

Wittig

Ph-P - ^ - C

. Ph CHQ

R = alkyl group or 2R- alkylene group

409884/1460.

The starting material can be (+) - or (-) - nerolidol in the form of its cis or trans isora or a mixture use of these isomers.

The reaction between nerolidol and N-bromosuccinimide is expediently carried out at around 20 ° C Temperatures, preferably carried out at about 18-20 ° C. The reaction time can be between about 27 and 170 hours. As for the other reaction conditions, the in HeIv. Chim. Acta j> 4, 461 (1971) use the method described.

The ozonolysis of the compound III can be carried out by methods known per se, e.g. at about -70 ° C in methanol will. As a reducing agent for the reduction of the ozonide, for example, methyl sulfide, triphenyl phosphine or else can be used Use trimethyl phosphite.

The acetalization of the aldehyde VI can be carried out by methods known per se. The acetal can be either be cyclic or acyclic.

The dehydrobromination of the acetal V can, for example, by means of sodium metal in a practically anhydrous Medium, e.g. in tetrahydrofuran, or by means of zinc powder in acetic acid.

The Wittig reagent, which is reacted with the aldehyde VII, can be prepared according to the method described in HeIv. Chim. Acta 50, 2W (1967) .

409884/1460

2,6, 10-trimethyl-10-hydroxy-dodeca ^, 6,11-trien-1-al can theoretically in the form of four configurational isomers, ie 'der'2c-is, 6cis-, 2eis, 6trans-, 2trans, 6trans and 2trans, 6cis isomers exist. However, the isomers with the cis configuration in position 2. The process according to the invention generally leads to mixtures of the 2trans, 6trans and 2trans _s 6cis isomers The ratio in which the two isomers are formed varies within certain limits and can be, for example, about 30 % 2trans, 6cis isomer to 70% 2trans, 6trans isomer. Since the two isomers have similar odor properties, it is not necessary to use them The mixture obtained by the process according to the invention can be used directly as a fragrance additive or fragrance component.

Instead of 2,6,10-trimethyl-10-hydroxy-dodeca-2,6,11-triene-1-al one can of course also precede it, e.g. its acetals, which under acidic conditions able to form the aldehyde, use.

In the following exemplary embodiments, the temperatures are given in degrees Celsius.

example 1

A perfume base was made by mixing the components listed below:

409884/1460

-9 Components 2431039 l, l-dimethyl - ^ - acetyl-6-
tert-buty1-indan Parts by weight Neroli bigarade 10 Undecenal 10 JS * 10 Nonadienal 1 % * ko Isobutyl salicylate 20th Citronellol UO Linalol 100 iso-methyl-a-ionone 100 Phenylethyl alcohol 100 Ylang 100 Oriental santal 60 Benzyl acetate HO Linalyl acetate 100 Methyl dihydrojasmonate 10 % * 100 Diethyl phthalate 80 Total 100 1000

* in diethyl phthalate

This perfume base developed an indefinite floral scent note. 100 parts by weight of Hydroxysinensal became 900 parts added to the perfume base. A perfume with a lily of the valley scent was obtained in this way. This perfume was particularly suitable good for scenting face creams.

For comparison purposes, 990 parts by weight of Perfume base mixed with 10 parts by weight of o-Sinensal. The received

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Fragrance! Composition developed an odor that was created by a intense citrus note was characterized. and no scent of lily of the valley exhibited.

Example 2

It was made a perfume base by mixing the following listed components:

Components . Parts by weight of nonanal 10% * . 10

ündecenal 10 % * 30

Dodecanal 10

Decanal 20

Methylnonylacetaldehyde 10 % * 30. Synthetic bergamot. 90 Oriental Santal 10

Phenylmethylcarbinylacetate 20 Tarragon 10 % * 30

Synthetic ambergris IO % * 50 Synthetic civet IO % * 20

Synthetic jasmine 70

Coumarin 30

Ketone musk 30

Ambrite Musk .20

Cyclopentadecanolide 10 % * 20

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-Io -

- 2431039 Entterpened orange oil 20th Vetyvery acetate 50 Vetyverol 50 Heliotropin i \ 0 Isoeugenol 30th Hexyl cinnamaldehyde 40 Synthetic Bulgarian
Rose oil 100 Synthetic rose absolutely 20th Ylang 80 iso-methyl-α-ionone 70 Vanillin 10 % * ■. 10 Total 1000

* in diethyl phthalate

This perfume base developed a warm and somewhat amber-like fragrance. 100 parts by weight of Hydroxysinensal were added to 900 parts by weight of the perfume base. The odor impression conveyed by this perfume composition was clearly better. While the floral notes of the perfume base were somewhat suppressed by the arabran note, the floral notes of the perfume composition came into their own. The addition of the Hydroxysinensai meant _s that the scent of the perfume composition had a special elegance.

If instead of Hydroxysinensal the same amount or even only one percent by weight of a-Sinensal for the perfume base

409984/1460

is given, so experience the olfactory properties of the . Perfume base a complete change. An intense fruity Fragrance note drowns out all other fragrance notes of the perfume base.

Example 3

A mixture of 44.1} g (0.2 mol) (±) -Nerolidol

(Mixture of cis and trans isomers), 37.4 g (0.21 mol) of N-bromosuccinimide and 500 ml of CGIn were stirred at 18-20 ° for 6 days. After adding petroleum ether (boiling range: 30-50 °) to the reaction mixture, the precipitate was filtered off. 0.5 g of sodium acetate was added to the piltrate, which was then concentrated at 10 torr. 63 g of 2-methyl-2-vinyl-5- (1,5-dimethyl-1-bromo-hex-4-en-1-yl) tetrahydrofuran (II) were obtained as residue. The latter was taken up in 630 ml of methanol. The solution was treated at -70 ° for 3 \ hours with an ozone-containing acid stream (total 0.2 mol 0-). The solution was kept at -70 ° and treated with a vigorous stream of nitrogen, whereupon 30 ml of methyl sulfide were added. The reaction mixture was allowed to warm to 20 ° under nitrogen over the course of 12 hours. The reaction mixture was concentrated at 10 torr, whereupon the residue was taken up in ether (2 separating funnels). The ethereal solution was washed three times with water and once with aqueous sodium chloride solution, then dried over magnesium sulfate and finally concentrated.

409884/1460

One obtained from 2-methyl-2-vinyl-5- (1-methyl-1-bromo-3-formyl-prop-1-yl) -tetrahydrofuran (III) existing backlog.

The residue was in a mixture of 250 ml

Benzene, 16.1 g (0.26 mol) of ethylene glycol and 100 mg of p-toluenesulphonic acid heated to boiling (using a Dean-Stark separator). After the formation of water has ended, heating was continued for 2 hours. then 100 ml of benzene were slowly removed by distillation. the The remaining solution was treated with 10% aqueous sodium carbonate (three times) and washed with aqueous saline (twice). By evaporating the solvent at 10 ^ orr the ethylene acetal (V) of the aldehyde (IV) was obtained as a residue.

The residue was dissolved in 150 ml of anhydrous tetrahydrofuran added, whereupon the resulting solution of a stirred suspension of 9 »65 g (0.42 mol) of powdered sodium in 500 ml d. the same solvent was added. After the reaction mixture had been stirred for a few hours at 20 °, its temperature rose spontaneously. The reaction mixture was kept at 40 ° for 6 hours (first by cooling and then by heating). Then an additional Ί.8 g (0.2 mol) of powdered sodium, suspended and 100 ml of tetrahydrofuran, added, followed by the reaction mixture over 15 hours was stirred at 40 °. After cooling, the liquid phase was carefully decanted off from the agglomerated sodium. Towards-

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if a small amount of ethyl alcohol were added to the liquid phase, the solvent was removed under reduced pressure and the residue was taken up in water. The solution obtained was extracted twice with ether. The ether extract was washed five times with water and then rapidly distilled at 0.001 torr. The distillate was fractionated again in a Vigreux column (30 cm; equipped with an adjustable reflux head). This gave 21.4 g (44.6 % based on nerolidol) of 4,8-dimethyl-8-hydroxy-deca-4,9-diene-1-al-acetal (VI), boiling point 97-105 ° / 0.001 torr. This product consisted of a mixture of the cis and trans isomers, which could be separated by distillation in a spinning band column. The cis isomer is more volatile than the trans isomer.

cls-acetal ¥ 1: d ^ ° = 0.9977 »np ° = 1.4816; IR (film): 920, 990, 1410, 1640, 3100 (-CH = CH ₂ ), 1140 (CO),

3470 cm " ¹ (OH);
MS -.- 1.'M ⁺ almost invisible with m / e 240, basic spade with

m / e 73 »
MKR: δ = 1.25 (3H, ει), 1.69 (3H, a broad), 1.30-2.30 (9H, m), 3.87 (4H, m) ,. 4.80 (IH, £, J = 4.5 Hz),.

4.88-5.35 (3H, m), 5.92 (IH, d / d, J = 17, J '= 10 Hz) ppm.

Calculated for C _llt H _2lt O ₃ : C 69.96 H 10.07 Ji Found: C 69.95 H 10.21 %

Ä09884 / 1460

trans-acetal VI: djj = 0.9975 »n £ = 1.1833;

IR (film): 920, 1410, 1640, 3100 (-CH = CH ₂ ), 1ΐ4θ (CO),

3 ^ 70 cm " ¹ (OH);
MS: M almost invisible at m / e 240, basic spade at

m / e 86;
MKR: δ = 1.25 (3H, s), 1.62 (3H, s broad), 1.30-2.30 (9H, m), 3.85 (4H, m), 4.80 (IH , t, J = 4.5 Hz), 4.88-5.35 (3H, m), 5.92 (IH, d / d, J = 17, Jt = ₁₀ Hz) ppm.

A solution of 4.85 g (20 mmol) of the cis or trans acetal VI in 120 ml of dioxane and 45 ml of 0.02 N sulfuric acid was heated to boiling temperature under nitrogen for 3 hours. The solution was allowed to cool to 20 ° and then 10 ml of 5% aqueous sodium bicarbonate were added. The reaction mixture was stirred for 15 min, after which the dioxane was removed. The residue was taken up in ether and the solution was washed with 5% aqueous sodium bicarbonate, three times with water and once with aqueous sodium chloride solution. Customary work-up and distillation gave 2.84 g (72 Jf) of cis- or trans-4,8-dimethyl-8-hydroxy-deca-4,9-dien-1-al (VII). cis-aldehyde VII: bp 83-85 ° / 0, 00 torr; djj ⁰ = 0.9661; τξ ° = 1.4828;
IR (film): 915, 990, l4lO, 1635, 3080 (-CH = _CH2), IIO5 (CO) ₃

I715 (C = O), 2720, 285Ο (-CHO), 345Ο cm " ¹ (OH); MS: M ⁺ invisible, M-18 with m / e I78, base spade with m / e 71;

409884/1460

MKR: δ. = 1.23 (3Η, s), 1.66 (3Η, s broad), 2.37 (3H,

m narrow), 1.30 to 2.50 (5H, m), 2.60 (IH, £, OH), 4,8O-5 ₉ 3O (3H, m), 5.88 (IH, d / d , J = 17, J «= 10 Hz), 9 _S 71 (IH, t, J = approximately 1.5 Hz) ppm.

trans-aldehyde VII: bp 93-95 ° / 0, 00 torr; djj ° = 0.9700;

τξ ° = 1.4800;

IR (film): 915, 990, 1410, 1635, 3080 (-CH = CH ₂ ), 1110 (CO),

1715 (C = O), 2720, 2850 '(- CHO), 3450 cm " ¹ (OH); MS: M ⁺ invisible, M-18 at m / e 178, base spade at m / e 71;

MKR: δ = 1.26 (3H, s) , 1.60 (3H, £ broad), 1.30-2.60 (9H, m), 4, βΟ-5.3Ο (3H, m), 5 .83 (IH, d / d, J = 17, J ¹ = 10 Hz), 9.32 (IH, t, J = approximately 1.5 Hz) ppm.

Calculated for C ₁₂ H ₂₀ O ₃ : C 73.43 H 10.27 %

Found: C 73.40 H 10.4l %

A mixture of 1.147 g (5.85 mmol) of cis-aldehyde VII, 1.95 g (6.14 mmol) of 1-formylethylidene-triphenylphosphorane and 12 ml of anhydrous benzene was heated to boiling temperature under nitrogen for 50 hours. The solvent was then removed under reduced pressure and the concentrate was taken up in a 1: 1 mixture of ether and petroleum ether (boiling range: 3Ο-5Ο ⁰ ). The solution was filtered and the filtrate was concentrated. The residue was distilled at 0.001 torr, boiling point 112 ° C. This gave 1.069 g (77.4 %) of 2,6,10-trimethyl-10-hydroxy-dodeca-2-trans, ocis-II-triene-1-al (I), which has the following physical properties

409884/1460

Features:

d ^ ° = 0.9577; n ^ ° = 1.5009;

IR (film): 915, 990, 1400, 3080 (-CH = CH ₂ ), 1100 (CO), 1635 (> C = C-CHO), 2700, 2850 (-CH0), 3450 cm " ¹ (OH) ;

MS: M invisible, M-l8 with m / e 218, intensive pragments with m / e 43 (basic spades), 55, 71, 93;

MKR: δ = 1.26 (3H, s), 1.70 (6H, £ broad), 2.62 (IH, a, OH), 1.30-2.80 (8H, m), 4.80 -5.40 (3H, m), 5.86 (IH, d / d, J = 17, J ¹ = 10 Hz), 6.43 (IH, t ₃ J = 6 Hz), 10.33 (IH, s) ppm. The latter signal (froton of -CHO) appeared at δ = 9.27 when the opinion was performed in FIG.

3.25 g (Iβ, 5 mmol) of trans-aldehyde VII and 5.53 g (17.4 mmol) of 1-pormylethylidene-triphenylphosphorane were reacted in 35 ml of anhydrous benzene in the manner described above. 3.6 g of crude product, boiling point 115-122 ° / 0.001 torr, were obtained, which was purified by chromatography on a column of 100 g of silica gel (Mallinckrodt, 100 mesh). Eluting with a 7: 3 mixture of benzene and ether gave 2.632 g (67.5 %) of 2,6,10-trimethyl-10-hydroxydodeca-2-trans, 6-trans-II-triene-1-al (I) , which had the following physical properties: bp 118-12O ° / O, 001 torr; djj ° = 0.9557; n ^ ° = 1.5009;

A0988A / U60

IR (film): 915, 990, 1400, 3080 (-CH = CH2), 1635, 1680 (> C = C-CH0), 2700, 2850 (-CH0), 3450 cm ^x (OH);

MS: M invisible, M-18 at m / e 218, intense fragments at m / e 43 (basic spade), 55, 935

MKR: 6 - 1.25 (3H, s) , 1.62 (3H, s wide), 1.71 (3H, s wide), 1.30-2.70 (8H, m), 2.50 ( IH, s, OH), 4.86-5.33 (3H, m), 5.91 (IH, d / d, J = 17, Jt = 10 Hz), 6.45 (IH, t, J = 6 Hz), 9.60 (IH, si) ppm. This latter signal (proton of -CHO) appeared at 6 = 9.27 when the measurement in CCIj. was carried out.

A09884 / 1A60

Claims (5)

PATENT CLAIMS. 1. Process for improving, amplifying or otherwise changing the olfactory properties of perfumes, perfumed Products and natural or synthetic essential oils, characterized in that one of the products mentioned an odor-changing amount of 2,6,10-trimethyl-10-hydroxy-dodeca-2,6,11-triene-1-al clogs. .2. Smelling product, especially perfume, perfumed product or natural or synthetic essential oil, characterized by a content of an odor-changing amount of 2,6,10-trimethyl-10-hydroxy-dodeca-2, 6, ll'-triene-l-al. 3. Fragrance composition, characterized in that one of its components 2,6,10-trimethyl-10-hydroxy-dodeca-2,6, lltrien-1-al is. 4. Perfume, characterized in that it is 2,6,10-trimethyl-10-hydroxy-dodeca-2,6, ll-triene-l-al and contains a diluent or carrier. 5. A process for the preparation of 2,6,10-trimethyl-10-hydroxy-dodeca-2,6, ll-triene-l-al, characterized in that N-bromosuccinimide is allowed to act on nerolidol (II) in order to 2 -Methyl-2-vinyl-5- (I ₄ 5-dimethyl-l-brora-hex-4-en-l-yl) -tetrahydrofuran CHI), the latter converted into its mono-ozonide and the ozonide to 2 -Methyl-2-vinyl-5- (l-methyl-l-brcm-3-formyl-prop-l-yl) tetrahydrofuran (IV) reduces the aldehyde 409884/1460 (IV) acetalized, first a reducing metal in a practically anhydrous medium and then water allowed to act on the acetal obtained (V), the 4,8-dimethyl-8-hydroxydeca - * », 9-diene-1-al- ace.tal (VI) hydrolyzed to obtain 4,8-dimethyl-8-hydroxy-deca-Jljii-dien-l-al (VII), and the latter subjected to a Wittig reaction with l-forifiyl-ethylidene-triphenylphosphorane to obtain 2,6,10-trimethyl-10-hydroxy-dodeca-Z _X 6,11-trien-1-al. The ,, patent attorney (Dr. JL Schmied-Kowarzik) 409884/1460