DE1768233A1 - Fragrance compositions and new Benzpyranabkoemmlinge for this - Google Patents

Description

. R. POSCHENRIEbER '.- ■■,. ■ $. -jJezeiibex 19.69 ·; . ■

DR. £. BOETTNER ..

DIPL-ING. H.-J. MÜLLER. P 17 68, -25.3.6

Patent attorneys * '''.-' ■ < ^: -

8 Munich so / son ■; - · 1768

Lucile-Grahn-Strasse 38 · ■ ·
Telephone 443? S5.

E. 77

Bush Boake Allen Limited,

20/42 Wharf Road, London HY 1 (Great ^Britain): ■ ·· ■■ ■■ ·; ■ '.'. ·

Fragrance compositions and new benzpyran derivatives therefor

The present invention "relates to fragrance compositions which" contain certain chemical compounds as Contain fragrance components. The invention also relates to such chemical compounds that hitherto have not yet been established, on methods of making the same and on a new way of working for the production of the previously known compounds.

Under the term. Fragrance compositions are understood to be substance lines which are obtained by mixing or composing a number of fragrances of synthetic or natural origin for the purpose of forming a fragrance concentrate. Such concentrates can be used alone or after appropriate dilution , but they are far more often added in small amounts to other materials in order to perfume them.

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prt ι i ι '. ■ - ». ν ..... '.-- u-And «» · »» Α * ΊΜ?

These perfumed materials include room sprays, Air fresheners, soaps, detergents, cosmetic and deodorant preparations and substrates such as talc, fabrics, fibers and paper products. Such concentrates (and also the aforementioned perfumed materials) are therefore commercial preparations, and the fragrance concentrates can consist of a simply composed or complex mixture of individual fragrance compounds.

The chemical compounds that make up the present invention concerned, are benzpyran compounds of the general formula,

(ι)

in which R _{1 is} an alkyl group having 1 to 4 carbon atoms and R "is a hydrogen atom or an alkyl group having ^: -1 to 4 carbon atoms. It can be assumed that all such compounds - with the exception of the first member of the series (in which R _{1 is} methyl and R _{2 is} a hydrogen atom) - have not yet been produced. These compounds can be prepared from β-ionone or its derivatives in general formula

109839/1790

(ID

getting produced.

ß-ionone (II; R ₁ = methyl, R ₂ ⁼ hydrogen) contains, if it has been prepared according to the previously known procedures, the acyclic double bond in the trans configuration with respect to the carbonyl group (as shown in formula II on this, cf. Naves, Barbier and Ardizio, Bull. Sog. Chirn., (5), 18, 247-250 (1951)), and of the derivatives of ß-ion, provided that they have been prepared according to the known working methods , one can also assume that they have this tear configuration, as shown in general formula II.

The action of electromagnetic radiation, for example ultraviolet light, on these trans- ß-jonons evidently converts them into cl ß-ß-ionons, which are unstable and spontaneously suffer a ring closure and thus a 2-R,. -3- ^ Hp- * 5,5,8a-! PrimetJiyl-5f6 _r 7,8 ^ tetrahydro-8a-H, 1-benz |) yran of the general formula I according to the following reaction scheme

! 09839/1790

(ID

Although the compound of the formula I, in which R _{1 is} a methyl radical and R "stands for a hydrogen atom, as has been described in the literature", can be obtained by irradiating β-ionone with ultraviolet light, cf. * Büchi and Yang, J. Amer Ghem. Soc. 7, 9 »2318-2323 (1957), nothing has been reported so far about their suitability as a fragrance. As has now been found, other benzpyrans of the formula I can be obtained in an analogous manner, and these compounds have one very pleasant smell, which makes them useful as a component of odorant compositions, which consist of a plurality of fragrance ingredients, valuable. moreover, since the trans -beta-ionones, which are used as starting materials, which themselves have characteristic and exploitable for fragrance compositions odors, needs its conversion into Benzpyrans not to have taken place completely, since mixtures of the benzpyran compounds with the ß-ionone starting materials even in the smells according to the invention off-compositions can find application. As was further found, the benzpyrans can also be obtained by a process which is in the thermal iso-

109839/1790

merization of the trans -β-ionone, the more volatile benzpyran (i) being slowly distilled off from the trans -β-ionone while it is kept under refluxing.

Accordingly, it is an object of the present invention to provide a fragrance composition which, as a Fragrance component an Eenzpyranverbindungen the general Formula.

(I)

contains in which R _{1 is} an alkyl group having 1 to 4 carbon atoms and Rp is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.

In a second aspect, the present invention relates to a 2-R ₁ -3-R ₂ -5,5,8a-trimethyl-5,6,7,8-tetrahydro-8a-H, 1-benzpyran of the general formula (i), however, where R _{1 is} an alkyl group having 1 to 4 carbon atoms and Rp is a hydrogen atom (except in the case where R _{1 is} a methyl group) or an alkyl group having 1 to 4 carbon atoms.

In a third aspect, the present invention relates to a process for the preparation of the compounds mentioned in the preceding paragraph, according to which a substituted trans-

109839/1790 ~ ⁶ "

ß-ion of the general formula

(ID

(in the R .. and Rp ^ ie defined in the previous paragraph Have meaning) an electromagnetic radiation, preferably the ultraviolet light, is exposed until at least 20% by weight, preferably at least 70% by weight, of the trans-β-ionone (II) has been converted into the corresponding benzpyran compound of the formula (I).

The invention finally relates in a fourth aspect to a process for the preparation of the compounds for a Use in the subject of the invention mentioned in the first place are determined, which consists in that one a substituted ß-ionone of the general formula

(II)

(in which R ₁ and Rp have the same meaning as defined in the explanation of the subject matter of the invention mentioned in the first place) ^{heated to 120 to 200 °} C. and a product from this at a suitable pressure

- 7th

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and distilled off a reflux ratio which is set so high that the isolated product at least 20 wt .- $ - preferably at least 50 wt .- $ - one Benzpyrans of the general formula

contains.

The benzpyrans according to the invention have valuable odor off properties. For example, the compound of the formula I in which E- is a methyl group and Ep is a hydrogen atom (which is derived from β-ionone) has a fragrance note, the meaning of which is to modify the wood character of the ionone; the compound of formula I in which each of the symbols R ₁ and R _? means a Fethylrest (which is derived from ß- iso -Methyl.ionon), has a strong 'oak moss bouquet; and the compound of the formula I in which Ry denotes an ethyl radical and R "denotes a hydrogen atom (which is derived from β-n-methylionone), is used as an extender for natural patchouli oil or as a component of synthetic patchouli oils. In addition, the benzpyrans of the present invention, as was further found, prove to be extremely effective for giving "body" to a composed fragrance composition so that they can be used in small amounts to

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"to round off" the overall composition; this effect is special easily recognizable in composed fragrance compositions of the "pichtennadel" type.

The β-ionone starting materials can be prepared according to generally known Procedures can be obtained in that one Oitral with the corresponding ketone, which in Fachbarstellung to the keto group must contain a methylene group, condenses and the resulting pseudo-ionone in the presence an acid, e.g. concentrated sulfuric acid, which is known to be far more likely to form the β-ionone compounds favored than those of the ot-ionic compounds, cyclized, this ring closure · usually carried out in a suitable solvent, 'such as petroleum ether will. These syntheses can be represented by the following general reaction scheme:

CHO

(Citral)

Methylene ketone

(pseudo-ionone derivatives)

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concentrated HpSO, in petroleum ether at O ⁰ C

(ß-ionone derivatives)

In the η series of the ß ^ -ionons, R _{1 is} a hydrogen atom or an alkyl group and Rp stands for alkyl, whereas in the iso series, which are formed in the reaction with a different Oc -methylene group, which is the particular ketone partner in the first Stage has ,, both symbols R ^ and Rp represent alkyl groups. The majority of these β-ionone derivatives are known compounds and, as already mentioned above, they are obtained in the form that their acyclic double bond is in the trans configuration with respect to the carbonyl group. -

The benzpyrans suitable for the purposes of the present invention can be obtained by the action of electromagnetic radiation on a β-ion of the formula II. Although the term "electromagnetic radiation", the irradiation of the substituted ß ^ ^ ionone with the radiation from a nuclear source or the use of X-rays covered with, the application is, of course, primarily ¹ of ultraviolet light in question. Strictly speaking, it is not necessary to dissolve the ß-ionone in a solvent, although this is for reasons of

- io -

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comfort is often done. The liquid β-ionone can be placed under a strong ultraviolet lamp and left there, Ms at least 20 i <> of this has been converted into the benzpyran, as is determined by periodic analysis, for example by means of infrared spectroscopy or nuclear magnetic resonance spectroscopy. The irradiation is preferably continued until at least a 70 " consecutive conversion to benzpyran has occurred, since this product is all the more valuable for incorporation into fragrance compositions, the higher its benzpyrane content.

The duration of the conversion by irradiation depends on the amount of treated ß-ionon, the strength of the radiation source and the temperature of the irradiation operation. The examples given below give indications of suitable ones Response times. The irradiation can take place at an elevated temperature, but the advantage of this is that compared to irradiation at room temperature is, as a rule, not so great that it requires the expenditure of additional heat in addition to the heat generated by the radiation source delivered, would justify. After the end of the irradiation, the reaction mixture of the Any solvent present is freed by stripping and by careful distillation under reduced pressure getting cleaned.

The benzpyrans suitable for the purposes of the present invention can also be obtained by a process of thermal

-. 11 -

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Isomerization can be obtained in which the trans -β-ionone is ^{heated to 120-200 0} C and slowly, ie using a high reflux ratio, is distilled over an effective fractionating column at an appropriate pressure, so that the isolated product is at least 20 percent by weight, preferably at least 50 percent by weight of the benzopyran. The thermal isomerization is preferably carried out under a reduced pressure such that the trans -β-Johon is in a refluxing state from which the desired product can be removed by distillation using a sufficiently high reflux ratio. The thermal isomerization is preferably performed at 140 to 15O ⁰ C and the distillation at a reflux ratio of at least 12 ϊ T, often around 20: 1 were carried out. If the benzpyran in the product isolated from this type of distillation does not have the desired purity, it can be further purified, for example, by rapid redistillation under reduced pressure.

The benzpyrans according to the present invention can be found in composed fragrance compositions in which they form one of the fragrance ingredients, technical application. The fragrance compositions are usually in liquid form or in the form of room sprays or in Aerosol form, but can also be used in soaps, detergents, cosmetic or deodorant preparations of all kinds mixed in or for the treatment of substrates such as talc,

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Fabrics, fibrous materials or paper materials can be used. The production of all these fragrance compositions comprises mixing or composing the benzpyrans according to the invention with at least one other fragrance. In fact, however, as is customary in the formulation of compositions of this type, normally a considerable number of fragrances are used in addition to the benzpyran. Besides, the Benzpyrans do usually only a small fraction of the fragrance composition, because of their desired fragrance properties come into play even in small partial quantities. Accordingly, the fragrance mixtures contain the present Invention usually 0.01 to 10 percent by weight, preferably 1.0 to 5.0 percent by weight, benzpyrans, based on the total weight of the fragrances or fragrances present.

The invention is now intended to be illustrated by the following examples Examples 1 to 4 illustrate the preparation of the new benzpyrans according to the invention and Examples 5-11 describe specific and representative fragrance compositions of the present invention.

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example 1 Thermal isomerization of ß-ionone

β-ionone (350 g) (II; R ₁ = methyl, R ₂ = hydrogen) was placed in a flask equipped with a 45.7 cm (18 inches) long distillation column with Fenski packing The entire device was then placed under a vacuum of 20 mm of mercury. The flask contents were heated to 145 to 15O ⁰ C, and distilled at a reflux ratio of 20: 1 from the product gradually. A distillate was obtained (280 g) which contained 65 i ° of a compound which, as indicated by infrared and nuclear magnetic resonance spectroscopy, consisted of a benzpyran of the formula I, where R _{1 is} a methyl group and R _{2 is} a hydrogen atom, and the could be further purified by renewed distillation. The benzpyran is characterized by an infrared spectrum with strong absorption bands at 1660, 1385, 1370, 1080-1120 and 785 cm " ¹ .

Example 2 Ultraviolet isomerization of ß-n-methyl.ionone

ß-n-Methyljonon (200 g) (II; R ₁ * ethyl, R ₂ = hydrogen) was dissolved in petroleum ether boiling from 80 to 100 ° 0 (2 liters) and the solution was irradiated for 14 days by a Hanau ultraviolet lamp Type PL 321 exposed ^{at 20 ° C.} The solvent was removed under reduced pressure.

- 14 109839/1790

- 14 - 1760233

Drifted, and the oil that remained contained, as was found, 75 % of the benzpyran of the formula I (R ₁ -ethyl, R ₂ = hydrogen) in addition to 25 $> not converted ß-n-methylionone. This mixture could be further purified by distillation under reduced pressure.

The infrared absorption spectrum was similar to that of the benzpyran prepared according to Example 1, but showed the presence of an ethyl group inoc-position to the oxygen atom in the pyran ring.

Example 3 Thermal isomerization of ß-n-methyl.ionone

β-n-Methylionon (172 g) was placed in a device of the type described in Example 1 and the vacuum was adjusted so that the contents refluxed at 155 ° C. When a reflux ratio of 20: 1 was set, a product slowly distilled off, and the distillate (140 g) contained, as could be shown, 90% of the benzopyran of the formula I (R ₁ = ethyl; Rp = hydrogen), which in its spectrograph Properties with those of the product described in Example 2 was identical.

Example 4 Ultraviolet isomerization of ß-isomethyl.ionone

The procedure of Example 2 was repeated using β-isomethyljonon (II, R ₁ = methyl, R ^ ■ methyl). Under the same conditions there was a transformation

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ORIGlNAL BATHROOM

of 70 io achieved. The conversion product was characterized by its nuclear magnetic resonance spectrum and its infrared spectrum, the latter spectrum having bands at 800, 1110-1145 (double bands), 1360-1390 (multiple ^{bands), 1600 and 1670 cm "1} (two strong bands) Spectra showed that the compound consisted of a benzpyran of the formula I in which both symbols R. and Rp represent methyl groups.

Examples 5-11

The following fragrance compositions were produced. Their scent notes corresponded to those given Types of perfume. The incorporation of the benzpyrans according to the invention in the specified small amounts practiced in in each case a clearly recognizable and pleasant perfume effect on the mixture, in so far as this the fragrance composition "body" and "rounded off" its perfume properties.

Vanillin Example 5 Weight steep Perfume Coumarin of the Ohypre type 10 Heliotropin 20th Musk ketone 30th Benzoin resinoid 40 Labdanum reainoid 50 5

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BAD ORiiaiNAL

Oak moss resinoid 20

Sandalwood Oil 60 Vetiverol. 50

Vetiveryl acetate 70

Patchouliol 30

Methyl ionone 30

'X-Jonon 10

Isoeugenol 10

Ylang oil 10

Bergamot oil 30

Rhodinol 15

Benzyl acetate 10

Tarragon oil 5

Benzyl benzoate 85

a benzpyran, as it is in j

of Examples 1 to 4 produced

has been 10

600

Example 6
Perfume of the continental

Versalid S (sold in stores 10 9 8 3 9/1790 20th - 17th ben from Gfivaudan Ltd.) 20th Coumarin 1OÖ ORIGlNAL BATHROOM Linaly acetate (pure) 10 Methyl nonylacetaldehyde 30th Amyl salicylate 10 Benzyl acetate 10 Clove oil to Geranium oil 40 Geraniol 100 Lavandin

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Petitgrain oil 60

Olehanum Resinoid 50

Patchouli oil 50

sweet orange oil 30

Thyme oil 10

Pile needle oil 440

a benzpyran as prepared in any of Examples 1 Ms 4 has been 10

1000

Example 7 Spruce-needle-type perfume

Weight steep 350 Picht needle oil 70 Bergamot oil 30th Mountain pine oil 5 Lauric aldehyde 535 Isobornyl acetate 10 a benzpyran like it
one of the examples 1
has been made in any-
Ms 4

1000

Example 8 ale Composition suitable for modern men’s perfume

parts by weight

AmbrettemoBchus 20

Coumarin 30

Vetiver oil 50

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. 18 -

Oak moss resinoid 10

Cedarwood Oil 50

(Jalbanum oil 5

Lemongrass Oil 50

Linalool 50

Phenylethyl alcohol 50

Orange oil (sweet) 30

Ylang oil 20

Lavandin oil 70

Petitgrain oil 70

Linalyl acetate 100

Bergamot Oil 100

Geraniol 100

Geranium oil 20

Benzyl benzoate 65

a benzpyran as prepared in any of Examples 1-4 been Bt 10

Example 9 Spruce needle-type perfume

900

Parts by weight

Isobornyl acetate 460 Linalyl acetate 70 Benzyl alcohol 50 Bergamot oil 50 Spruce needle oil 200 Coumarin 20th Terpineoi 100 dae produced in Example 1

Benzpyran 50

1000 109839/1790 - 19 -

Example 10 -Type Ethylene brassylate 10 Perfume from "Hirtal Cologne" Parts by weight Virsalid S (commercially available
from Givaudan Ltd.) 30th Coumarin 30th Vetiveryl acetate 20th Vetiver oil 30th Oak moss resinoid 20th 10% methyl nonyl acetaldehyde
(dissolved in ethyl phthalate) 30th Galbanum oil
Citral dimethyl acetal
Linalool 10
?8th sweet orange oil 50 Phenylethyl alcohol 80 Ylang oil premiere 30th Lavandin oil 70 Petitgrain Oil (Paraguay) 100 Linalyl acetate 100 Nerol 100 Bergamot oil 150 that prepared in Example 1
Benzpyran 50

1000

Example 11 Perfume des

Weight steep - 20th Patchouli Oil (Penang) 20th Oak moss resinoid 10 Cardamom oil ¹ O

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Tarragon oil 10 Coumarin 50 Versalid S (sold in stores
from the company G-ivaudan Ltd.) 30th Clove bud oil 30th Roson 20th Eenzyl acetate 50 Lavandin oil 150 Phenylethyl alcohol 50 Linalyl acetate 150 Amyl salicylate 50 Terpineol 50 Geraniol 70 Geranium oil 30th Ylang oil 20th Linalool 70 Diethyl phthalate 80 the benzpyran of formula I.
(R ₁ = methyl, R ₂ »hydrogen) 50 1000

- Patent claims -

- 21 -

1 0 9 8 J 9/1 7 9 0

Claims (1)

Claims before 1. Fragrance compositions, characterized ^ indicates that it is a benzpyran compound of the general formula in which R _{1 is} an alkyl group having 1 to 4 carbon atoms and Rp is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. 2. fragrance compositions according to claim 1, characterized in that that they also have such other fragrance ingredients that are used to achieve the scent of the spruce needle contribute, included. 3. A 2-R ₁ -3-R ₂ -5,5,8a-trimethyl-5,6,7,8-tetrahydro-8a-H, 1-benzpyran of the general formula given in claim 1, characterized in that R _{1 is} an alkyl group having 1 to 4 carbon atoms and Rp is a hydrogen atom (except in the case in which R ₁ is methyl) or is an alkyl group having 1 to carbon atoms. 4. A process for the preparation of a benzpyran compound as claimed in claim 3, characterized in that a substituted trans -ß-ionone of the general formula - 22 - 109839/1790 (in which R ^ and Rp have the meaning given in claim 3) exposed to electromagnetic radiation, preferably ultraviolet light, until at least 20 percent by weight, preferably at least 50 percent by weight, of the trans -β-ionona have been converted into the said benzpyran compound. Process for the preparation of a benzpyran compound intended for use in the composition according to Claim 1, characterized in that a substituted trans-ß-ionone of the general formula (in which R ₁ and R _{2 have} the meanings given in claim 1) heated ^{to 120 to 200 0} C and a product is distilled off using a reflux ratio that is so high that the isolated product is at least 20 $>, preferably at least 50 #, which contains the named benzpyran compound. 109839/179 0 - 23 ORIGINAL BATHROOM 1 7 G ο 2 3 6. The method according to claim 5, characterized in that the trans-ß-ionon is ^{heated to 140 to 150 0} C, 7. The method according to claims 5 and 6, characterized in that that a reflux ratio of at least 12: 1 is used. 109839/1790 / 'bad oksinal