DE2538790A1 - POLYCYCLIC FRAGRANCES - Google Patents

Description

Our reference: O. Z, 31 512 Rr / Be 6700 Ludwigshafen, 29 * 8.1975

Polycyclic ^ fragrances

The invention relates to Diels-Alder adducts in general Formula I.

(D,

in which R and R stand for -H or -CH, or else R and R ² together stand for a further bond between the carbon atoms carrying them and X and Y each stand for -CH ₂ OH, -CH (OH) -CH ₅ , -COOH, -COOCH ,, -COOC ₂ H ₅ , -CHO, -CO-CH ,, -CO-C ₂ H ₅ or -CN, or X and Y together mean -CO-O-CO-, or else one of the two letters X or Y stands for -H or -CH, and the other has the meaning given above.

The new polycyclic Diels-Alder adducts are characterized by valuable fragrance properties. They have green, fresh, fruity, sometimes woody odor nuances with very long-lasting adhesion and / or fixing properties. They can be used as a component of ₁ perfumes and in compositions for perfuming personal care products such as soaps, shampoos, hair lotions, detergents and other consumer products. They are also suitable for flavoring food and tobacco.

The invention further provides a process for preparing the novel compounds of the formula I, which is characterized in that the new 8-vinyl-tricyclo [5,2, l, 0 ² 'JDEC 8-ene of the formula II

(H)

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with a dienophile of the general formula III

R ¹ f

C = C ^ (HI), X Y

1 ρ
in which R and R for -H or -CH, or else

1 2
R and R together represent a further bond between the carbon atoms carrying them and X and Y each denote -COOH, -COOCH ,, -COOC ₂ H ₅ , -CHO, -COCH ,, -COC ₂ H ₅ or -CN or X and Y together represent the group -CO-O-CO-,

or one of the two letters X or Y stands for -H or -CH, and the other has the meaning given above, in an is known to submit to a Diels-Alder reaction.

1 2 The new Diels-Alder adducts of the formula I, in which R and R stand for -H or -CH, and one of the two letters X or Y stands for -CH ₂ OH or -CH (OH) -CH, and the others for H are obtained by reducing the corresponding oxo compounds in a manner known per se.

The new 8-vinyl-tricyclo-

5,2,1,0 'dec-8-en can be prepared in a simple manner known per se by elimination of water from 8-vinyl-tricyclo [5,2,1,0'-decan ^ 8-ol be prepared, which in turn by reacting the readily available tricyclo [5,2,1,0 'J decanon-8 with a vinyl magnesium halide can be obtained in a simple manner according to Grignard. Instead of the diene II, the 8-vinyl-tricyclo- [5,2,1,0 'I-decan-8-ol can be used as a starting material, however, more stringent reaction conditions are necessary, e.g. higher temperatures and / or acidic catalysts. The yields are therefore often lower.

Suitable dienophiles of the formula III are:

a) Alkenes with only one activating substituent, i.e. so

1 2 compounds of the formula III in which R and R are -H or -CH- * stand, one of the letters X or Y -COOH, -COOCH ,,

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-COOC ₂ H ₅ , -CHO, -CO-CH ₅ , -CO-C ₂ H ₅ or CN, and the other letter X or Y stands for -H, that is, simply α, β-unsaturated aldehydes, ketones, Nitriles, carboxylic acids or carboxylic acid esters.

Examples include: acrolein, methacrolein, crotonaldehyde, Methyl vinyl ketone, pent-2-en-4-one, acrylonitrile, methacrylonitrile, croton nitrile, acrylic acid, methacrylic acid, crotonic acid and the methyl and ethyl esters of the 3 acids mentioned. The aldehydes, ketones and nitriles mentioned are preferred.

b) Alkenes with two activating substituents, i.e.

1 2 bonds of the formula III in which R and R are -H or -CH ,, in particular are -H and X and Y are each -COOH, -COOCH ₃ , -COOC ₂ H ₅ , -CHO, -CO- CH ₃ , -CO-C ₂ H ₅ or -CN, or X and Y together represent the group -CO-O-CO-. Examples include dimethyl fumarate, diethyl fumarate and maleic anhydride.

- c) Alkynes with only one activating substituent, i.e. therefore

1 2 Compounds of formula III, in which R and R together represent a further bond between the carbon atoms carrying them, one of the letters X or Y for -COOH, -COOCH ₃ , -COOC ₂ H ₁ -, -CHO, -CO-CH ₃ , -CO-C ₂ H ₅ or -CN and the other is -H or -CH ₃ .

Examples include propiolaldehyde (propinal), butyn- (2) -al, propiolic acid, tetrolic acid (butyn- (2) acid) and the methyl and ethyl esters of the acids mentioned.

d) alkynes with two activating substituents, i.e. compounds

1 2

gene of formula III, in which R and R together represent a further bond between the carbon atoms carrying them and X and Y each represent -COOH, -COOCH ₃ , -COOC ₂ H ₅ , -CHO, -CO-CH ₃ , -CO-C ₀ H ₁ - or -CN.

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Examples include acetylenedicarboxylic acid and its methyl and ethyl esters.

The dienophiles of the formula III are generally known and commercially available compounds.

The alkenes described under a) with only one activating substituent are preferably used as dienophiles of the formula III.

To carry out the Diels-Alder reaction is generally 'a mixture of 8-vinyl-tricyclo ß, 2, l, 0' I dec-8-en (II), the dienophile of the formula III and optionally an inert solvent for the Reaction time brought to temperatures from 0 to 150 ⁰ C, preferably from 50 to 80 ⁰ C. The reaction time is about 1 to 200 hours, depending on the type of dienophile. The dienophile is generally used in about 0.5 to 10 molar amount, preferably in about 2 to 5 molar amount, based on II.

The reaction mixture is used to avoid possible resinification generally a small amount, i.e. about 10 to 100 mg per mole of II, of one of the most common for Diels-Alder reactions lent stabilizers, like hydroquinone, too.

The reaction can be carried out without a solvent or in an inert solvent.

Examples of inert solvents that can be used are: aliphatic hydrocarbons such as pentane, hexane and cyclohexane or hydrocarbon fractions; aromatic hydrocarbons, such as benzene, toluene or xylene; Chlorinated hydrocarbons such as methylene chloride, chloroform or chlorobenzene ether, such as diethyl ether, dipropyl ether, diisopropyl ether, tetrahydrofuran and anisole; Alcohols such as methanol, ethanol, propanol, Isopropanol and cyclohexanol; Ketones such as acetone, methyl ethyl ketone and methyl isopropyl ketone; Amides, such as dimethylformamide, Dimethylacetamide and hexamethylphosphoric acid triamide or nitro compounds, such as nitromethane and nitrobenzene, or mixtures of the solvents mentioned. -5-

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The reaction is carried out either without pressure or under the autogenous pressure of the reactants in closed reaction vessels.

The reaction mixture is worked up in a customary manner, for example by distillation. For further details on Diels-Alder reactions, we refer to R. Sauer, Angew. Chem. J ^ (1907) * pages 77 to

The Diels-Alder adducts generally fall as mixtures of several Isomer. Depending on the spatial sequence of the addition, when using unsymmetrical olefins of the formula III 8 stereoisomeric Diels-Alder adducts possible. The attack of the dienophile can be "meta" or "ortho" to the Cg of the diene Formula II take place, "exo" or "endo" and from above or from below. The general rules of the Diels-Alder reaction and Analogous examples with vinylcyclohexenes or vinyl bicyclenes (see A. S. Onishchenko "Diene Synthesis", Israel Program for Scientific Translation, Jerusalem 1964, pp 410-445, in particular Pages 410 to 413 and pages 423 to 425) leave as Main product expect the "ortho-endo" isomer, in the example of acrolein the isomers,

respectively.

in the first case a "from below" attack, in the second case there is an "from above" attack. A prediction of the real With the complex stereochemistry of diene, attack is difficult and decisive from the exo / endo position of the 5-ring addicted. When using symmetrical olefins and alkynes as dienophiles of the formula III, the number of possible stereoisomers is lower.

The stereoselectivity of the reaction can be increased by working at as possible low reaction temperatures and / or by addition

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Catalytic amounts of Lewis acids such as BF. ,, AlCX ,, ZnCl ₂ etc. are increased (lc in particular page 84).

If the reaction is carried out in the presence of catalytic amounts of a Lewis acid such as AlCl ,, EF ,, SnCl ₁ , or ZnCl ₂ , the procedure is as described above, but at lower temperatures, ie at temperatures from about -80 to +20 ⁰ C, preferably -40 to ⁰ ° C. The amount of catalyst is between 0.1 and 10 #, preferably between 0.5 and 5 $>"based on starting II.

Carbonyl compounds can be reduced in the alcohols by numerous standard processes, e.g. by catalytic hydrogenation, by reduction with the help of metals or metal hydrides or by electro- or photochemical reduction. For further details, see S. Patai, "The Chemistry of the Hydroxyl Group", Interscience Publishers

1971, pages 231 to 24 ?. In Example 3, the reduction of a carbonyl compound with a metal hydride (NaBH ₁ ) is described.

The new polycyclic Diels-Alder adducts are characterized by valuable fragrance properties. They have green, fresh, fruity, sometimes woody odor nuances with very long-lasting adhesion. They also have fixing properties. They can be used as a component of perfumes and of compositions for perfuming personal care products such as soaps, shampoo, hair lotions, detergents and other consumer products. The odor is somewhat dependent on the stereochemistry (exo / endo ratio) of the tricyclo | 5 * 2, ^{1.0 3} J decan-8-one used; in general, the adducts obtained from the commercial ketone are sufficient for the application.

example 1

16.0 g (0.10 mol) of 8-vinyl-tricyclo | ^, 2, l, 0 ²ⁱ⁶ ^ | dec-8-en, 11.2 g (0.2 mol) of acrolein, 10 mg of hydroquinone and 100 ml of toluene are ^{kept at 90 °} C. for 3 hours. The reaction product is washed three times with 50 ml of water and distilled. From 110 to

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115 ° C / 0.1 Torr go over 19.2 (89 % of theory) of an aldehyde mixture.

Odor: waxy, green-peeled, peach, fixing. The gas chromatogram shows 2 compounds in the ratio 89: The -H nuclear magnetic resonance spectrum shows 2 aldehyde signals at / 9.60 and 9.69 in the ratio 85:15, some smaller signals, and an olefinic proton at <5.34. Analysis and molecular weight are consistent with the empirical formula. The -C spectrum makes the structure I with R ¹ , R ² ■ -H, X = -CHO, Y = -H probable for the main component.

Example 2

16 g (0.1 mol) of 8-vinyl-tricyclo [5.2, ^1.02i6 ] dec-8-ene, 11.2 g (0.2 mol) of acrolein, 50 ml of toluene and 10 mg of hydroquinone are 150 Held at 20 to 25 ° C for hours. Working up as in Example 1 gives 19.4 g (90 % of theory) of an aldehyde mixture which, according to gas chromatography and nuclear magnetic resonance spectroscopy, contains the same two aldehydes as in Example 1, but in a ratio of 92.5: 7.5.

Example 3

To 4 g of sodium borohydride in 200 ml of ethanol, the solution of 21.6 g (0.1 mol) is added to the aldehyde mixture obtained in Example 1 in 30 ml of ethanol at 25 ⁰ C within 60 minutes and the reaction mixture 3 hours at 25 ° C touched. The ethanol is then distilled off, the residue is taken up in ether, acidified with 10 percent sulfuric acid to pH 3, the organic phase is concentrated and distilled. From 111 to 115 ° C / 0.5 Torr, 16.2 g (74 % of theory) of an alcohol pass over which, according to the analytical data and the nuclear magnetic resonance spec-

1 2 trum probably has the formula I, in which R, R and Y are -H and X is -CH ₂ OH.

η ²⁵ : 1.5368

Odor: similar to aldehyde, weaker, but lasts much longer.

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example

21.6 g (0.1 mol) of the aldehyde mixture obtained according to Example 1, 50 ml of methanol and 1 g of Raney nickel are ^{treated together with hydrogen at 100 °} C. and 100 atmospheres until no more hydrogen is absorbed. In the subsequent work-up by distillation, 19 * 8 g of a waxy, solidifying alcohol mixture distill off at 1.55 to 1.56 ° C / 0.1 Torr, the main product (approx. 80 %) of which, according to the analytical data and the H and C nuclear magnetic resonance spectrum, has the structure

having.

nJ3 ⁵ : 1.5285

The yield is 95 % of theory,

Example 5

A solution of 8.0 g (0.05 mol) of 8-vinyl-tricyclo, dec-e-en, 10.6 g (0.2 mol) of acrylonitrile, 50 ml of toluene and 10 mg of hydroquinone is heated to 80 ° for 12 hours C heated. The reaction mixture is then cooled, washed twice with 3> 0 ml of water, concentrated and distilled. From 125 to 128 ° C./0.2 torr, 8.1 g (corresponding to 76% of theory) of an 80:20 mixture of nitriles pass over. Analytical and spectroscopic

1 Data make the formula I, in which R, R and Y stand for -H and X stands for -CN, probable for the main product.

ng ⁵ : 1.5325

Smell: fresh, flowery, slightly fruity (lime), good adhesion.

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Example 6 ^f

If one works analogously to Example 5, but uses 0.2 mol of crotonaldehyde instead of 0.2 mol of acrylonitrile, 7.2 g (corresponding to 62.5 % of theory) of a Diels-Alder adduct are obtained

1 2
of formula I, in which R and R stand for -H and one of the letters X or Y stands for -CH, and the other stands for -CHO, from boiling point 112 to 115 ° C / O, O5 Torr and the refractive index η ²⁵ : 1.5290.
Smell: coniferous, woody, like vetiver oil, good adhesion.

Example 7

If one works analogously to Example 5 * but uses 0.2 mol of methacrolein instead of 0.2 mol of acrylonitrile, 8.3 g (corresponding to 72 % of theory) of a Diels-Alder adduct of the formula I in which R ^{2 is} - CH ,, Y is -CHO and X and R ^{1 are} -H or R ^{1 is} -CH ₃ , X is -CHO and R ² and Y are -H are from bp 105 to 106 ° C / O, 0.5 Torr and the refractive index η ²⁵ ; 1.5292,

Smell: spruce, woody, fresh, slightly fruity.

Example 8

If one works analogously to Example 5 * but uses 0.2 mol of ethyl acrylate instead of 0.2 mol of acrylonitrile, 9 * 5 g (corresponding to 73 % of theory) of a Diels-Alder adduct of the formula I in which one of the letters is obtained X or Y is -COOC ₂ Hc and the other radicals are -H, boiling from 117 to 121 ° C / 0.05 Torr and refractive index n ² ^: 1.5152. Odor: slightly minty, green.

Example 9

If one works analogously to Example 5 * but uses 0.2 mol of methyl vinyl ketone instead of 0.2 mol of acrylonitrile, 10.8 g (corresponding to ^ k% of theory) of a Diels-Alder adduct are obtained

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of the formula I, in which one of the letters X or Y stands for. -CO-CH, stand and the other radicals -H mean, from the boiling point 115 to 120 ° C / 0.05 Torr and the refractive index n ²⁵ : 1.5259.
Smell: herbaceous, fruity (strawberry), earthy, good adhesion.

Example 10

If one works analogously to Example 5 * but uses 0.2 mol of ethyl propiolate instead of 0.2 mol of acrylonitrile, 9 * 2 g (corresponding to 71 % of theory) of a Diels-Alder

1 2 adduct of the formula I, in which R and R form another bond and Y = H, X = COOC ₂ H ₁ -, from boiling point 128 to lj50 ° C / 0.1 Torr and from the refractive index n ^: 1 odor : weak, musty.

Example 11

16 g (0.1 mol) of 8-vinyl-tricycloI5,2,1, O ² ' ⁶ J dec-8-en, 19.6 g (0.2 mol) of maleic anhydride, 50 ml of toluene and 10 mg of hydroquinone are 70 Held at 20 to 25 ° C for hours. Working up as in Example 1 gives 9 * 5 g (corresponding to 75 * 5 of theory) of a Diels-Alder adduct of the formula I in which

1 2 the letters X and Y mean -COOH and R and R -H, from boiling point 153-157 ° C / O, O5 Torr and n ^ ⁵ - 1.5 * 12, which has good fixing properties.

Example 12

17.8 g (0.1 mol) of 8-vinyl-tricyclo j-5,2, l, 0 ^{2 '6} J-decan-8-ol, 19.6 g (0.2 mol) of maleic anhydride and 80 ml of xylene are heated to 160-180 ° C. for 5 hours. Working up the reaction mixture as in Example 1 gives 18.2 g (corresponding to 68 % of theory) of an adduct with a boiling point of 158-163 ° C / 0.05 Torr,

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Claims (1)

Claims 1 2
in which R and R stand for -H or -CH, or else 12 s R and R together for another bond between them carrying carbon atoms and X and Y are each -CH ₂ OH, -CH (OH) CH- ,, -COOH, -COOCH ,, -COOC ₂ H ₅ , -CHO, -CO-CH ₃ , -CO-C ₀ H ₁ - or -CN or X and Y together denote -CO-O-CO-2 5 or one of the two letters X or Y is -H or -CH, and the other has the meaning given above. 2. Diels-Aider adducts of the general formula I. <n 1 2 in which R and R are -H or -CH, and one of the letters X or Y is -CHO, -CO-CH ,, -CO-C ₂ H ₅ or -CN and the other is -H. -12-70981 1/1 UO _Page 12 0 _# Z, Jl 512 3 «Process for the preparation of the new compounds of the formula I according to claim 1 » daduroh characterized in that 8 * vinyl * ttfieyolo [5,2,1, O ² ' ⁶ Ί deo * 8-en of the formula II (II) with a dienophene of the general formula III 1 2>. ^ Sun - oZ you). in which R and R _{stand for -H or -CH 5} , or R and R together stand for a further bond between the carbon atoms carrying them and X and Y are each -COOH, -COOCH ,, -COOC ₂ H ₅ , -CHO, -COCH ,, -COCpHe or -CN, or X and Y together represent the group -CO-O-CO-, or but one of the two letters X or Y stands for -H or -CH, and the other has the meaning given above, is subjected to a Diels-Alder reaction in a manner known per se and in the event that X and / or Y stands for - CH ₀ OH or CH (OH) CH, the corresponding compound in which X and / or Y is -CHO, -COCH ,, ^ COOR, reduced in a manner known per se. k " Process for the preparation of the new compounds of the formula I according to Claim 1, characterized " that 8-hydroxy- 8 * vinyl * trioyolo [5.2 _<l i _# 0 ² '^] deoftn of the formula IV CCk / ™ OK 70981 1/1140 O.Z. 31 512 with a dienophile of the general formula III R ¹ in which R ¹ and R ^{2 represent} -H or -CH ,, or R ¹ and R ² together represent a further bond between the carbon atoms carrying them and X and Y each signify -COOH, -COOCH ,, -COOC ₂ H ₅ , -CHO, -COCH ₅ , -COC ₂ Hc- or -CN, or else X and Y together represent the group -CO-O-CO - Stand, or one of the two letters X or Y stands for -H or -CH ^ ₅ and the other has the meaning given above, subjected in a known manner to a Diels-Alder reaction and in the event that X and / or Y stands for -CH ₂ OH or -CH (OH) CH ₃ , the corresponding compound in which X and / or Y stands for -CHO, -COCH-z, -COOR, reduced in a manner known per se. BASF Aktiengesellschaft 1 " 70981 1 / 1U0