DE2256483C3 - 5-Phenyl-3-methyl-pent-2-en-1-acid nitrile, process for their production and their use as odoriferous substances - Google Patents

Description

CH ₂ -CH ₂ -C-CHj

in which R has the meaning given in claim 1, with cyanoacetic acid in the presence of a weak basic catalyst and the resulting isomer mixture with a strong base in the ^ -unsaturated compounds isomerized

3. Use of the unsaturated nitriles according to claim 1 as fragrances.

The invention relates to 5-phenyl-3-methyl-pent-2-en-I-acid nitriles of the formula

CH ₃ CH ₂ -CH ₂ -C = CH-CN (I)

Hydrogen atom or one of its use as

in the R for a
Ci-Gä-Alkylrest is, as well
Fragrances.

R preferably represents hydrogen. The C1-C3-AI-kylrest is the methyl, ethyl, n-propyl or isopropyl radical

The compounds of the formula I according to the invention can be in the cis form and in the trans form.

The invention further relates to a process for the preparation of the unsaturated nitriles of the formula I, which characterized in that one benzylacetones the formula

CH; - CH ₂ -C-CH ₃

inventive method z. B. Ammonia, Ammoniomsaize, primary or secondary amines, pyridine, piperidine or quinolm, preferably ammonium acetate Find pyridine and piperidine use.

The reaction of benzyl acetone with cyanoacetic acid is expediently carried out in an organic solvent. Can be used as a solvent advantageously find those use that form azeotropic mixtures with water, such as Benzene hydrocarbons, preferably benzene, toluene or XyIoL

If the weakly basic catalysts used for the process according to the invention are also used represent a solvent that works with water

azeotropic mixture forms e.g. B. pyridine and piperidine, the reaction can also be carried out in this medium. Mixtures of the solvents mentioned can also be used.
The reaction temperature is not critical and can generally vary between about 20 and 180 ⁰ C. The reaction is expediently carried out in the boiling range of the solvent used in each case. The water formed in the condensation reaction can be removed by azeotropic distillation with the solvent. It has to be

Proven to be expedient to terminate the reaction if the solvent distilled off is not water contains more

The reaction components cyanoacetic acid and benzyl acetone or alkyl-substituted benzyl acetone can generally be used in approximately equimolar amounts, but can be used for improvement the yield, the cheaper starting component in each case, even in a slight excess of up to about 0.5 mol, based on the more expensive starting material in each case, can be used.

The weakly basic catalyst used for the process according to the invention can, for. B. in amounts of about 0.01 to 2 mol, based on 1 mol of cyanoacetic acid, are used.

After the water formed in the reaction has been completely separated off, the solvent becomes and optionally also the weakly basic catalyst is distilled off.

The unsaturated nitriles according to the invention, for. B. by fractional vacuum distillation, received pure.

In the reaction of the benzylacetones with cyanoacetic acid, an isomer mixture is obtained which, in addition to the compounds of the formula I according to the invention, also includes the compounds of the formulas formed by shifting the double bond from the (^ -position into the β, γ- and JJ.y'-position II and III contains, in which R has the meaning given under formula I.

CH ₃
CH ₂ -CH = C-CH ₂ -CN (II)

in which R has the meaning given under formula I, reacts with cyanoacetic acid in the presence of a weakly basic catalyst and isomerized the resulting mixture of isomers with a star base into the "^ -unsaturated compounds
As weakly basic catalysts for the, -CH ₂ -C-CH ₂ -CN (III) mixtures, which according to the method according to the invention

Ren, for example, can consist of the following compounds:

trans-5-phenyl-3-meAyl-pent-2-en-l-acid nitrile,

cis-S-Phenyl-S-methyl-pent ^ -en-l-säiu-enitriL

trans-5-phenyl-3-methyl-pent-3-en-1-acid nitrile

cis-S-phenyl-S-methyl-peut-S-en-1-acid nitrile and S-phenyl-S-methylenepentanoic acid nitrile

or from the p-methyl, substituted on the benzene nucleus p-ethyl, p-n-propyl or p-isopropyl derivatives named compounds a

From the mixture of isomers it is possible to obtain the desired "^ -unsaturated compounds usual preparative methods, e.g. by fractionated Distillation or preparative gas chromatography, isolate, according to the invention, however, the mixture of isomers is treated with a strong base, e.g. B. alkali hydroxides or alkali alcoholates into the «, jS-unsaturated Compounds isomerized

Alkali metal alcoholates are preferably used for the isomerization such as sodium methylate, sodium ethylate, sodium propylate or sodium butylate are used in particular Sodium methylate is preferably used.

The isomerization is expediently carried out in a solvent that is inert to the reaction components solvent, for example Can be used are the alcohols corresponding to the alcoholates used, such as methanol, Ethanol, propanol, butanol, particularly preferably methanol.

The base can be used in amounts of 0.01 to 10 mol, based on 1 mol of the isomer mixture used, are used, preferably in amounts of 0.1 to 1 mol.

The reaction temperatures used for the isomerization are, for example, -80 up to + 120 ° C, preferably at 0 to 50 ° C

The reaction mixture is under the stated conditions until complete isomerization in generally stirred or shaken for 1 to 50 hours. It has proven to be particularly advantageous, for example proved, when using 0.1 to 1 mol of base, a reaction time of about 1 to 5 hours to be observed.

The corresponding mixture is obtained in this way from the mixture used for isomerization «^ -Unsaturated compounds according to formula I. The« ^ -unsaturated compounds are generally included as mixtures of the respective cis-trans isomers, the cis and the trans isomers z. B. in proportion from about 1: 1 to about 1: 3. For example is when using a base concentration of about 1 mole per mole of unsaturated compound im Reaction mixture and a reaction time of about 3 hours a cis-trans isomer mixture in the ratio formed from about 2: 3 to 2: 5, which as a mixture is particularly valuable in terms of perfumery.

The cis-trans isomer mixture obtainable by the process according to the invention can be used as such for Perfumery purposes can be used or by simple separation methods into the cis and trans isomers be separated. Separation methods which have proven to be advantageous are, for example, fractionated Distillation over packed columns or split tube columns or preparative gas chromatography. the isolated cis and trans isomers open opposite the cis-trans isomer mixtures further perfume

see application possibilities through differentiated scent notes.

The unsaturated nitriles according to the invention draw are characterized by particularly advantageous, desirable fragrance properties that are radiant, intense, can be characterized firmly and harmoniously a They enrich the perfume materials that were previously available for building up agrumen and fruit notes valuable fragrances.

The application of the previously common citrus fragrances, such as B. Citral and CitronellaL is associated with the disadvantage that these substances over against aggressive media, especially acidic media such as B. hair care products or acidic cleaning agents, are inconsistent. The agro-fragrances used up to now, which are resistant to aggressive media, such as B. Geranium acids are essential in their olfactory properties not satisfying. For example, geranium acid nitrile has a strong, aggressive note of nitrile In addition, the adhesive strength leaves something to be desired.

In contrast, the compounds according to the invention have excellent fragrance properties. Instead of the unpleasant metallic nitrile note of geranonitrile, those according to the invention have Compounds have a soft and warm citrus flavor. Compared to the well-known lemon fragrances is the adhesive strength improved many times over. In compositions can be a new fresh and long-lasting Citrus note can be achieved in aggressive media The unsaturated nitriles according to the invention also show no discoloration use in aggressive media.

The compounds according to the invention can be used in

pure form or in the form of isomer mixtures can be used as uniform fragrances. You can also in mixtures with other substances in fragrance compositions e.g. in amounts of about 0.01 to 25 percent by weight are used, preferably in amounts of about 0.1 to 10 percent by weight, based on the total mix.

The field of application of the compounds according to the invention is due to the harmonious odor type and the application properties, such as E.g. the stability against aggressive media, unusually large. They are suitable for use in perfume compositions for numerous finished products in cosmetics, fine perfumery, detergents and technical sector, e.g. B. for detergents, washing powder, Soaps, dishwashing detergents, fabric softeners, bubble baths, shampoos, detergents, hair care products, Hair dyes, cold wave agents, cold wave fixatives, antiperspirants, bath salts, deodorants, Powders and creams.

example 1

1120 ml of toluene. 622 ml of pyridine, 21 g of ammonium acetate, 936 g (6.32MoI) benzylacetone and 608 g (7MoI) cyanoacetic acid (98%) were in a 4-liter two-necked flask equipped with an internal thermometer and water separator with intensive condenser for 5 hours Boiling heated. The solvent mixture was then distilled off.
The distillation residue was cooled to room temperature and a solution of sodium methylate, which had been prepared by reacting 40 g (about 1.75 mol) of sodium in 1.751 methanol, was added. The mixture was stirred for 3 hours at room temperature,

then neutralized with 105 g (1.75 mol) of acetic acid and the solvent was distilled off with stirring. the The distillation residue was added to 1 liter of ice water / poured, the organic phase that forms separated off and fractionally distilled in vacuo S This gave an iron first run of about 120 g of benzyl acetone and at 94 to il2 ° C / 03mmHg 856 g (5MoI, corresponding to 79.1% yield based on benzyl acetone) of a mixture of ds- and trans-5-phenyl-3-methyl-pent-2-en-1-acid nitrile, where cis and to trans isomers were present in a weight ratio of 2: 3.

Refractive index: η ³ S = 1.534;

Density: at 25 ° C 097;

Smell: soft citrus-rose-like with aldehydic woody and musky nuances.

Example 2

In the same way as in Example 1, 1110g (632 mol) p-ethyl-benzylacetone instead of 936 g (632 moles) benzyl acetone with 7 moles cyanoacetic acid implemented This gave 916 g (4.6MoI) of a mixture of cis and traris-5- (p-ethylphenyl) -3-methyl-pent-2-en-1-acid nitrile, where cis and trans isomers were present in a weight ratio of 2: 3.

Boiling point: 107 to 114 ° C / 0.5 mm Hg;

Refractive index: n? = 1.530;

Density at 25 ° C: 037;

Smell: green citrus note with fruity and rose-like shade.

Example 4

In the same way as in Example 1, 1200 g (632MoI) of p-iso-propyl-benzylacetene were used in place of 936 g (632 mol) of benzyl acetone reacted with 7 mol of cyanoacetic acid. 1024 g (4.8 mol) of one were obtained Mixture of cis and trans-5- (p-iso-propylphenyl) -3-methyl-pent-2-en-1-acids, where cis and trans isomers were present in a weight ratio of 2: 3.

Boiling point: 110 to 116 ° C / 03 mm Hg;

Refractive index: π S ¹ = 1325;

Density at 25 ° C: 035;

Smell: sweet, citrus-mirabelle-like, fruity with a very soft, fine wood note and rose nuance.

• 5

In the same way as in Example 1, 1024 g (632 mol) p-methylbenzylacetone instead of 936 g (632 mol) benzylacetone with 7 mol cyanoacetic acid implemented This gave 870 g (4.7 mol) of a mixture of cis and trans-5- (p-methyl-phenyl) -3-methyl-pent-2-en-1-acid nitrile, where cis and trans isomers were present in a weight ratio of 2: 3.

Boiling point: 104 to 112 ° C / 03 mm Hg;

Refractive index: η? = 1330;

Density at 25 ° C: 037;

Smell: green citrus rose note with a fruity woody nuance.

Example 3

35

40 methyl-pent-2-en-1-acid nitrile, with cis and trans isomers in a weight ratio of 2: 3.

Boiling point: 113 to 120 ° C / 03 mm Hg;

Refractive index: ng "= 1324;

Density at 25 ° C: 0.954;

Smell: sweet, fruity, lemon, rose-like and woody nuances.

Example 6

725 g of the mixture of cis- and trans-5-phenyl-3-methyl-pent-2-en-1-acid nitrile obtained according to Example 1 were heated to the boil in a 1 liter flask and in a 1 m packed column with an inner diameter of 3 cm, which was charged with 350 g Wilson spirals with a diameter of 2.0 mm and which was provided with a column head for adjusting the reflux ratio to 5: 1, subjected to the fractional distillation. The fractions obtained ^a C with a vacuum of 0.2 Torr 88-89 ° C and 92-95 were fractionated twice over the same column. 45 g of cis-5-phenyl-3-methyl-pent-2-en-isotonitrile with a constant boiling point of 82 ° C. at 0.15 torr and 62 g of trans-5-phenyl-3-methyl-pent-2 were obtained -en-1-acid nitrile obtained with a constant boiling point of 94 ° C at 0.20 Torr.

Refractive index

cis -5-phenyl-3-methyl-pent-2-en-1-acid nitrile

/ κ = 1.531,
trans-S-phenyl-S-methyl-pent ^ -en-1-acid nitrile η = 1.537.

odor

The fragrance properties of the cis and trans forms are different from one another. The cis-5-phenyl-3-methyl-pent-2-en-1-acid nitrile has in addition to the citrus component of the cis-trans mixture an indeterminate fruity acetamide asparagus note. The trans-5-phenyl-3-methyl-pent-2-en-i-acid nitrile has a very fine citrus note.

45

Example 7

200 g of the mixture of cis- and trans-5-phenyl-3-methyl-pent-2-en-1-acid nitrile obtained according to Example 1 were heated to the boil in a 250 ml flask and passed through an 80 cm long standardized can which was provided with a column head to adjust the reflux ratio to 10: 1, distilled. About 40 g of cis-5-plienyl-3-methyl-pent-2-en-isoic acid nitrile with a constant boiling point of 82 ° C at 0.15 were thereby Torr and about 60 g of trans-5-phenyl-3-methylpent-2-en-l-acid nitrile obtained with a constant boiling point of 88 ⁰ C at 0.15 Torr. The refractive index and fragrance properties were identical to the results found in Example 6.

Example 5

In the same way as in Example 1, 1200 g (6.32 mol) of p-n-propylbenzylacetone were used in place of 936 g Reacted (6.32 mol) of benzyl acetone with 7 mol of cyanoacetic acid. This gave 960 g (4.5 mol) of one Mixture of cis- and trans-5- (p-n-propylphenyl) -3-

Example 8

In a gas chromatograph, 10 μΐ of the samples 2 to 5 were measured in 20 runs obtained cis-trans isomer mixtures separated preparatively into the pure cis and trans isomers.

The following amounts of cis and ns isomers were obtained in pure form:

) Separation of the mixture of cis and trans-5- (p-methylphenyl) -3-methyl-pent-2-en-1-acid nitrile

from example 2: S

70 mg of cis -5 (p-methylphenyl) -3-methyl-pent-2-en-1-acid nitrile;

Refractive index: / ?? = 1.527;

Smell: herbaceous, rosy, citrus note, spicy clove note; 90 mg trans -5 (p-methylphenyl) -3-methyl-pent-2-en-1 acid nitrile;

Refractive index: /? -: = 1.532;

Smell: green, citrus-like, geranium-like, spicy. ) Separation of the mixture of cis and trans-5- (p-

Ethylphenyl) -3-methyl-pent-2-en-1-acid nitrile from

Example 3:

64 mg of cis-5- (p-ethylphenyl) -3-methyl-pent-2-en-isonitrile.

Refractive index: η = 1.528; Smell: herbaceous, spicy, fruity, lemon 88 mg trans-5- (p-ethylphenyl) -3-methyl-pent-2-en-1-acid nitrile;

Refractive index: /? · = 1.533;

Smell: citrus note, rosy, spicy.

) Separation of the mixture of cis and trans-5- (p-n-propylphenyl) -3-methyl-pent-2-en-1 acid nitrile

Example 5:

75 mg of cis -5 (p-n-propylphenyl) -3-methyl-pent-2-en-1-acid nitrile; Refractive index: /; = 1.522;

Smell: spicy, citrus note, fruity; 92 mg trans-5- (p-n-propylphenyl) -3-methyl-pent-2-en-1-acid nitrile:

Refractive index: /? = 1.527;

Smell: fruity, citrus note, rosy, woody. I) Separation of the mixture of cis- and trans-5- (plsopropylphenyl) -3-methyl-pent-2-en-1 acid nitrile from Example 4:

70 mg of cis -5 (p-isopropylphenyl) -3-methyl-pent-2-en-1-acid nitrile;

Refractive index: / ?; = 1.524;

Smell: fruity, mirabelle plum, floral-jasmine, citrus note;

94 mg of trans-5- (p-isopropylphenyl) -3-methyl-pent-2-en-1-acid nitrile;

Refractive index: / ?? = 1.527;

Odor: f void, citromg, flowery, rosy, woody.

Example 9

a) Perfume composition using the product mixture from Example 1 (formulation I) : important parts

Bergamot oil Lemon oil Orange oil bitter Petitgrain oil Mandarin oil Clary sage oil

Hydroxycitronellal ix-hexyl cinnamaldehyde

Geranium oil

Sandalwood oil, East Indian Vetiveryl acetate

Patchouly oil

Ethylcitrone jlyl oxalate Product mixture from example 1 00

55

60 by addition of the product mixture from Example 1, the present formulation was a fresher and rounded note which could not be achieved without the addition of the mixture of Example. 1 The fresh and rounded note was retained right through to the after-smell and lasted for an exceptionally long time compared to conventional agrumen notes.

b) Perfume composition using the

Product mixture from example 2

In recipe I, instead of 25 parts of the product mixture from Example 1, 25 parts of the product mixture were used from Example 2 incorporated. Compared to the corresponding formulation without the inventive Compounds a very fresh, natural smell occurred due to the addition of the product mixture from Example 2 Lemon note, which stuck into the after-smell.

c) Perfume composition using the

Product mixture from example 3

In recipe I, instead of 25 parts of the mixture from Example 1, 25 parts of the product mixture were used from Example 3 incorporated. Compared to the corresponding formulation without the inventive Compounds obtained by adding the product mixture from Example 3, this recipe a fresh, agrumige note, which was also clearly noticeable in the aftertaste.

d) Perfume composition using the

Product mixture from example 4

In recipe 1, instead of 25 parts of the product mixture from Example 1, 25 parts of the product mixture were used from Example 4 incorporated. Compared to the corresponding formulation without the inventive The addition of the product mixture from Example 4 resulted in particularly long-lasting compounds citronige. somewhat orange-like note.

e) Perfume composition using the

Product mixture from Example 5

In recipe I, instead of 25 parts of the product mixture from Example 1, 25 parts of the product mixture were used from Example 5 incorporated Compared to the corresponding formulation without the formulation according to the invention Compounds emerged in the initial odor an agrumigen, citric note, especially in the after-odor causes a pleasantly fresh effect

A cologne perfumed with the perfume compositions according to Examples 9a) to 9e) was as follows composed: 4 percent by weight of perfume oil of the formulation I according to Examples 9a) to 9e), 96 percent by weight of 80% ethyl alcohol.

Example! 0

A perfume composition that can be used for perfuming suitable for soap, had the following composition:

Parts by weight 6 trimethylundecylenealdehyde 240 α-hexylcinnamaldehyde

36 styrene acetate

67 phenylethyl alcohol

36 tetrahydrogeraniol

25 amyl salicylate

25 ylang-ylang oil 191 p-tert-butylcyclohexyl acetate

12 clove oil

60 cedar wood oil, Moroccan 50 vetiverylacetai:
36 patchouly oil
24 cinnamon alcohol

6 oak moss absolute
60 Benzoin Sumatra Resin
36 Galaxolide (1,3,4,6,7,8-hexahydro-4,6,6,7,7,8-hexamnethyl-cyclopenta j> -2-benzopyran)
48 coumarin
36 Mixture of Example 1

* 5

1000

The addition of the product mixture from Example 1 gives the perfume composition the rosy-woody scent note a lively, citrus-like-green, very fresh tip that persists in the further course of the fragrance.

100 g of soap shavings were mixed with 1 g of the perfume composition mixed until a soap mass of practically homogeneous composition was obtained. After homogenization, the soap mass was pressed into a bar of soap.

Example 11

A perfume oil that is suitable for perfuming detergents was made according to the following recipe II composed:

Parts by weight

45 Trimethylundecylenaldehyde, 10% solution in

Diethyl phthalate
418 phenylethyl alcohols
150 tetrahydrogeraniol

45 eugenol methyl ether

60 cinnamon alcohol, 10% solution in diethyl phthalate

12 hex-3-en-l-ol

30 tetrahydrolinalool

30 Λ-ion

60 Trichloromethylphenylcarbinylacetate 150 Mixture from Example 1
1000

In this recipe, the addition of the product mixture from Example 1 changes the pure rose bouquet of the corresponding recipe without this product mixture to a freshly flowered complex which is interesting in terms of perfumery. At the same time, the adhesion is significantly improved

A fabric softener consisting of the Ingredients:

Parts by weight

6.7 dimethyl distearyl ammonium chloride approx

75% technical goods 0.5 allyl alcohol polyglycol ether, 12 moles of ethylene oxide

containing

0.2 perfume oil of formulation II 92.6 water, distilled 100.0

60

was prepared according to the following: ^2/3 of the water were at 70 to 8O ⁰ C. and the dimethyl distearylammoniumchlorid and Allylalkoholpolyglykoläther dissolved therein with stirring The remaining water was added and stirred to long, cooled until the batch at 45 ° C was. Then the perfume oil was added and stirring was continued until it was evenly distributed. Um Aufrah

35

To avoid 40 mung or skinning, was allowed to cool as temperature product in a covered container on Zimmertem.

Example 12

A hair treatment emulsion was produced according to the following recipe: First, a Mi Schung A and a mixture B made of the ingredients listed below (quantity information ben in parts by weight):

Mixture A

0.20 emulsifier fatty alcohol polyglycol ether based on oleyl alcohol with about 10 moles of ethylene oxide

0.80 emulsifier fatty alcohol polyglycol ether based on oleyl alcohol-cetyl alcohol with about 5 mol Ethylene oxide

3.00 cetyl alcohol

0.50 Wollfettalkoholoxäthylat with about 10 MoI

Ethylene oxide
20.00 water, distilled

Mixture B

71.80 water, distilled
0.20 sorbic acid
0.50 lauryl pyridinium chloride
0.40 citric acid
5.00 sorbitol 700% aqueous solution 0.30 polyvinylpyrrolidone
0.30 product mixture from example 1

The product mixture from Example 1 covers the basic note of the basic recipe with a fresh, citrus-green scent.

Preparation of Mixture A

All components were mixed with stirring at 7O ⁰ C

Preparation of the mixture B

The sorbic acid was dissolved with stirring at 90 ⁰ C in the INAE ^u-water. The solution was allowed to cool to C. At this temperature, the remaining constituents of the mixture were added with stirring.

Mixture B was added with stirring to the mixture A, wherein prior to mixing, the Mi-M c? ^U K ^g η ^eme temperature of 70 ⁰ C and the ΖΛϊ r ^{Uf "a Tenj} Peratur of 55 ° C set! SSi ^{b 1} S? ^{B Λε} mixture with further stirring ^{m wc} ^ cooling and then homogenized.

Example 13

. ine were mixed with 1 g of Produktgess · -. Example 1 mixed until a 7tm, "" TT ^"oF P ^raktisch homogeneous Zusammensetzimg was obtained after homogenization was

the serf mass pressed into a bar of soap friS ⁶ . u ^ ^{tene soap was} distinguished by one

with a radiant, citrus-rose-like smell emerged from a certain cosmetic note.

Example 14

) iel 13 was used instead of 1 g des Sche ^ «£" "" «* from Example 1 1 g of the product mixture from Example 2 is incorporated into a soap corn The soap obtained in this way was distinguished by a -non citric, fresh, somewhat fruity-flowery

Example 15

According to Example 13, instead of 1 g of the Product mixture from Example 1 1 g of the product mixture from Example 3 incorporated into a soap mass

The soap obtained in this way was distinguished by a fruity, citric, fresh odor.

Example 16

According to Example 13, instead of 1 g of the product mixture from Example 1, 1 g of the product mixture

Sches from Example 4 incorporated into a soap mass.

The soap obtained in this way was distinguished by a faintly aggravated odor.

Example 17

According to Example 13, instead of 1 g of the Product mixture from Example 1 1 g of the product mixture from Example 5 is incorporated into a soap mass.

The soap obtained in this way was distinguished by a slightly fruity odor.

Claims (2)

Patentoinsveröche: 1. S-phenyl-S-methyl-pent ^ -en-l-acid nitrile der formula -CH ₂ -CH ₂ -C = CH-CN in which R stands for a hydrogen atom or a Ci-Ca-alkyl radical is% 2. Process for the production of the unsaturated Nitriles according to Claim 1, characterized in that benzylacetones of the formula