The invention relates to novel odorants. namely Schiff bases.

In particular, the invention is concerned with the compounds of the formula

wherein

R signifies CH ₃ . C ₂ H ₅

R 2 signifies H. CH, R signifies H. C ₁ _ ₄ -alkyl

R , R , R ,

R signify H, CH_ , C_H_ , CH_CH_CH_ ,

CH(CH ) . 3 2 X signifies methylene. ethylidene, propylidene. ethylene. propylene, 2.3-butylidene,

Ur/10.4.91

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4 5 6 total number of carbon atoms of R , R . R ,

R . < 6

Accordingly, tetralins and indanes are embraced by formula I.

The compounds of formula I are distinguished by very natural notes in the direction of musk. Worthy of mentioning is in particular a frequent combination of musky and flowery notes, this combination of notes being of particular interest because of the resulting powerful body notes. Concerning the flowery notes, the orange blossom and tuberose aspects may in particular be mentioned.

They exhibit good substantivity. especially in fabric softenes and detergents.

They are not only suited in odorant compositions of the flowery, but also of many other types, especially those suited in the field of the luxury perfumery.

The compounds of formula I are obtained as the essential reaction products of a process comprising reacting an carbonyl compound of formula

with an alkyl anthranilate of formula

- 3 -

The convenient process parameters are as follows:

Temperature: ca. 30°C to 150°C

Pressure: from ca. 1 atm. down to 20 mmHg

Solvents: not necessary

Molecular proportions of Il/lll: ca. 1:2 to ca. 2:1, with ca. 1:1 being preferred

Catalysts: acids, e.g. organic acids such as p-toluene sulfonic acid. Lewis acids, such as BF . etc., molecular sieves of the acid type

Working up: (concentration by) distillation off starting materials under reduced pressure, then crystallization of the residue; or utilization of the residue as such. The crystallizatio is effected using solvents such as heptane or ethanol, etc.

The carbonyls II can also be used in the form of their acetals of ketals. namely the derivatives of the formula

see for example EP 0379981 (A ), formula I for the definition of the radicals and the preparation of such derivatives.

The novel Schiff bases combine with numerous known odorant ingredients of natural or synthetic origin, whereby the range of the natural raw substances can embrace not only readily-volatile, but also moderately-volatile and slighhly- -volatile components and that of the synthetics can embrace representatives from practically all classes of substances, as will be evident from the following compilation:

Natural products, such as tree moss absolute, basil oil. citrus fruit oils (such as bergamot oil, mandarin oil, etc.), astix absolute, myrtle oil, palmarosa oil, patchouli oil. petitgrain oil Paraguay, wormwood oil.

alcohols, such as farnesol, geraniol, linalool, nerol, phenylethyl alcohol, rhodinol. cinnamic alcohol,

® aldehydes, such as citral. Helional . α-hexyl- cmnamaldehyde. hydroxycitronellal, Lilial ®

(p-tert.butyl-α-methyl-dihydrocinnamaldehyde). methyl- nonylacetaldehyde,

ketones, such as allylionone. α-ionone. β-ionone, isoraldein (isomethyl-α-ionone) . methylionone.

- esters, such as allyl phenoxyacetate. benzyl salicylate. cinnamyl propionate. citronellyl acetate, citronellyl ethoxolate (citronellyl) . O -CO -CO . OC 2_H-5.), decyl acetate, dimethylbenzylcarbinyl acetate, dimethylbenzyl- carbinyl butyrate. ethyl acetoacetate, ethyl acetyl- acetate, hexenyl isobutyrate, linalyl acetate, methyl dihydro asmonate. styrallyl acetate, vetiveryl acetate. etc..

lactones. such as γ-undecalactone.

various components often used in perfumarv. such as musk ketone, indole, p-menthane-8-thiol-3-one, methyleugenol.

The Schiff bases can be used in wide limits which can range in compositions, for example, from about 0.1 (deter¬ gents) - about 20% (alcoholic solutions), without these values being, however, limiting values, as the experienced perfumer can also achieve effects with even lower concentra¬ tions or can synthesize novel complexes with even higher amounts. The preferred concentrations range between about 1 and about 10%. The compositions manufactured with I can be used for all kinds of perfumed consumer goods (eau de cologne, each de toilette, extracts, lotions, creams, shampoos, soaps, salves, powders, toothpastes, mouth washes, deodorants, detergents, fabric conditionsers, tobacco, etc.).

The Schiff bases can accordingly be used in the manufac¬ ture of compositions and - as the above compilation shows - using a wide range of known odorants or odorant mixtures. In the manufacture of such compositions the known odorants referred to above can be used according to methods known to the perfumer such as e.g. from W. A. Poucher, Perfumes. Cosmetics and Soaps 2_. 7th Edition. Chapman and Hall. London. 1974.

Examples

1- Method A

Into a three necked reaction flask equipped with a stirrer, a thermometer, a water trap and a condenser, 0.5 moles of aldehyde or ketone II is added to 0.5 moles of alkyl anthranilate III.

The vacuum is adjusted to 100 mmHg and the reactor is heated slowly to 100°C. then maintained at 120-130°C until the reaction does not progress any more. (The reaction is

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monitored by GC and ^" " ^" H NMR) . The reaction mass may be used as that or it is distilled under vacuo to remove any starting materials still present.

The following products have been prepared according to this method A,

employing Methyl anthranilate (MA), or ethyl anthranilate

11)

under vacuo (120 mmHg)

The reaction mass is used crude without any purifica¬ tion. The yellow liquid mixture contains 30% of aldehyde. 5% of methyl anthranilate. and 65% of the Schiff Base (methyl- -N-[(1.1.4.4-tetramethyl-tetralin -6-yl)methylidene]- -anthranilate) . Confirmation by GC analysis (conditions: 25 meters x

0.32 mm. OV (stationary phase) 101 programmed at 140-220°C at 4°C per minute); in agreement with H NMR (200 MHz): 9.96 ppm, s; 3.88 ppm. s; 8.23 ppm. s; 3.84 ppm. s. Odour: honey-like, "oranger" flower (orange blossom), musky, powerful and soft.

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2 )

under vacuo (120 maHg)

The reaction mass, a yellow liquid contains 30% of aldehyde. 10% of methyl anthranilate. and 60% of the Schiff base (methyl-N-[(1.1.4,4,7-pentamethyl-tetralin -6-yl)methy- lidenej-anthranilate) .

H NMR (200 MHz): 10.2 ppm. s; 3.88 ppm. s; 8.45 ppm. s; 3.86 ppm, s.

Odour: powdery, polycyclic musk-like, floral (oranger flower) .

³ >

under vacuo ( 120 πaiHg)

The crude product is crystallized with heptane as solvent and gives after filtration a white solid (mp 63-73°C) containing: 37% of aldehyde, 15% of methyl anthranilate, and 48% of the Schiff base (methyl-N-[(1,1.3, 4, ₄ -pentamethyl-tetralin -6-y1)methylidene]-anthranilate. H NMR (400 MHz): 9.96 ppm, s; 3.84 ppm. s; 5.71 ppm. broad s; 8.24 ppm, s; 3.87 ppm. s.

Odour: flowery, musky, woody, oranger.

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)

under vacuo ( 120 mmHg)

The reaction mass is a yellow liquid containing: 40% of aldehyde. 10% of methyl anthranilate. and 50% of the Schiff base (methyl-N-[ (1.1.2,4, .7-hexamethyl-tetralin -6-yl)raethylidene]-anthranilate) .

H NMR (200 MHz): 10.2 ppm, s; 8.50 ppm, s; 3.85 ppm, s; 3.88 ppm, s. Odour: musky, powdery, floral (oranger flower).

5 )

under vacuo ( 120 cssHe)

The reaction mass is a yellow liquid containing: 15% of aldehyde. 10% of methyl anthranilate. and 75% of the Schiff base (raethyl-N-[ (1, 1.2.3 ,3-pentamethyl-indan -5-yl)methyli- dene]-anthranilate and raethyl-N-[ (3-ethyl-l.1.3-trimethyl- -indan -5-yl)methylidene]-anthranilate) .

H NMR (200 MHz): 9.98 ppm, 2s; 3.87 ppm. s; 8.27 ppm. s; 3.84 ppm. s. Odour: musky, floral (oranger flower).

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6 )

under vacuo ( 50 πunHg)

The reaction mass is distilled under vacuo (0.05 mmHg) to remove the starting material and the residue is a green liquid containing 35% of aldehyde, and 65% of the Schiff base (raethyl-N-[ (l.1.4,4-tetramethyl-tetralin -6-yl)methyl- -methylidene]-anthranilate) .

H NMR (200 MHz): 2.57 ppm. s; 2.15 ppm, s; 3.78 ppm. S. Odour: flowery (oranger flower)

7)

under vacu o ( 120 mmHg)

The. reaction mass is a yellow liquid containing: 25% of aldehyde, 5% of ethyl anthranilate, and 70% of Schiff base (ethyl-N-[(l.1,4,4-tetramethyl-tetralin -6-yl)methylidene]- -anthranilate) .

H NMR (200 MHz): 9.95 ppm, s; 4.29 ppm. quadruplet; 8.22 ppm, s. Odour: honey-like, oranger-flower, musky.

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)

under vacuo (120 mmHg)

The reaction mass is crystallized out of heptane and gives a white solid mixture (mp 50-60 ^β C) containing: 20% of aldehyde. 5% of ethyl anthranilate, and 75% of the Schiff base (ethyl-N-[1.1.3.4,4-pentamethyl-tetralin -6-yl)methyli- dene]-anthranilate) .

H NMR (200 MHz): 9.95 ppm. s; 5.7 ppm, broad s; 8.24 ppm, s; 4.3 ppm. quadruplet. Odour: vanilla-like, slightly musky.

Method B

About 40 g of molecular sieve (Linde 5 A) are added to 0.10 moles of ketone and 0.12 moles of alkyl anthranilate in 40 ml of toluene. The reaction mixture is shaken between 20 and 80°C until the formation of ketimine does not progress any more. The reaction is monitored by GC and H NMR (200 MHz) .

The mixture is then seperated from the molecular sieves and the latter are washed with toluene. Solvent is removed from the filtrate by rotary evaporation and the crude is purified by vacuum distillation or crystallization.

The following products have been prepared according to this method B.

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9 )

•iOh. SO'C-→-TO'C

The crude product is distilled under vacuo (0.5 mmHg) to remove the starting material and the residue is crystallized out of ethanol. By this way a pure white ketimine is obtained (methyl-N-[(1.1.2.4,4.7-hexamehyl-tetralin -6-yl)- methyl-methylidene]-anthranilate) . rap 111-112°C, GC 100%, H NMR (400 MHz): 2.5 ppm, s; 2.12 ppm. s; 3.84 ppm. s. Odour: floral (oranger flower), fresh.

10)

A vacuum distillation provides a pure ketimine (methyl-N-[(1.l-dimethyl-6-tert-butyl-indan -4-yl)methyl- -methylidene]-anthranilate) , bp 150°C, under vacuo (0.2 mmHg) GC 100%. H NMR (400 MHz): 2.16 ppm, s; 3.81 ppm. s. Odour: Yara-yara (β-naphthol methyl ether, i.e. intensely sweet, orange blossom-acacia like).

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Method C

Into a reaction flask equipped with a stirrer, a thermometer, an alcohol trap and a condenser. 0,1 mole of ketal or acetal II' of the carbonyl compound II is added to 0,05 mole (generally: from ca. 0,05 mole to ca. 0,1 mole) of alkyl anthranilate III. The vacuum is adjusted to 120 mm Hg and the reactor is heated slowly to 100°C, then maintained at 100-110°C until the reaction does not progress anymore. (The reaction is monitored by GC and H NMR) . The reaction mass is then cooled and may be used as such without any purification step or it is distilled under vacuo to remove any starting materials still present. The following products have been prepared according to this method C. employing methyl anthranilate (M.A.)

The reaction mass is a yellow liquid containing : 55% of schiff base (methyl-N-[(1,1.3.4.4-pentamethyl-tetralin

-6-yl)-methylidene]-anthranilate) , 44% of 6-(forrayl-diethyl- -acetal)-l.l,3,4,4-pentamethyl-tretralin and 1% of 6-formyl- -1.1.3,4,4-pentaraeth l-tet alin.

Confirmation: by GC analysis (conditions : 25 meters X 0.32 ram, OV 101 (stationary phase) programmed at 140°C-220°C at 4°C per minute); the structure is in agreement with H

- 13

NMR (80MHZ):

9.96 ppm. s; 5.44 ppm, s; 3.77 ppm. s; 8.20 ppm. s;

Odour: Flowery, musky, slightly woody.

Example 11

Odorant composition parts by weight parts b wei

Cedar wood oil Benzyl acetate Geraniol extra Isoraldeine (methyl ionone) Phenylethyl alcohol Hydroxycitronellal Benzyl salicylate Hedioπe

(methyldihydrojasmonate) Hexyl cinnamic aldehyde Cetonial (Helional) cis-Hexenyl salicylate LRG 1201 Evernyl (Benzoic acid 3,4-dihydroxy- 3,6-dimethyl-methyl ester) 5.00 5.00

Clove oil 8.00 8.00

Heliotropine crist. 8.00 8.00

Mandarine oil 15.00 15.00

Phenyl acetaldehyde 2.00 2.00 n-Undecylenaldehyde

(1% in Carbitol) 2.00 2.00

Methyl-N-[(1,1.3,4. -penta- methyl-tetralin-6-yl)- methylidene]-anthranilate/ 7-Formyl-l,1,2, ,4-penta- methyl-tetralin 60.00

Dipropylene glycol 60.00

In this white flower accord, in particular suited for Eaux de toilette, the multifacet odour (musk, orange blossom) contributes to the esthetics of the perfume, in particular in as fer as the musk note is concerned.

Odorant composition

Allyl cyclohexyl propio

Styrallyl acetate

Isoeugenol Geranium oxide 10%

Verdyl acetate

Dimetol

Petitgrain essence Para

Linalool Benzyl acetate

Geranyl acetate

Phenylethyl alcohol

Hexyl cinnamic aldehyde

Bergamote essence Methyl-N-[(l,1.3.4.4-penta- methyl-tetralin-6-yl)- methylidene]-anthranilate/

7-Formyl-l.1.2,4,4-penta- methyl-tetralin 50.00 Dipropylene glycol 50.00

The above formula is in particular suited for shampoos, and the compound of example 3 enhances in particular the body notes of the formulation.