CH637359A5 - 8-EXO-HYDROXYMETHYL-ENDO-TRICYCLO (5.2.1.O (2,6)) - DECANE DERIVATIVES. - Google Patents

Description

This invention relates to original tricyclic compounds, and more particularly to 8-exohydroxymethyl-endotricyclo- (5.2.1.02'6) -decane derivatives, that is to say esters and ethers of formula (I):

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wherein R represents a saturated or unsaturated alkyl group of 1 to 5 carbon atoms, an acyl group of 1 to 5 carbon atoms or a glycidyl group; these compounds and a group ROH2C— are combined at position 8 of a norbornane ring on the exo side.

It has already been described in previous publications that certain derivatives of tricyclo- (5.2.1.02-6) -decane, produced from endo-dicyclopentadiene, are used as a perfuming agent in certain perfumes (Japanese Laid-open Publications Nos 25340/1974 and 9014/1976, and Japanese Laid-open Applications Nos 84558/1975 and 70036/1977).

The inventors have discovered that 4-homo-isotwistane-3-amine and its hydrochloride have antiviral properties (Japanese Laid-open Application No. 18830/1977). Other research has been carried out to synthesize the precursor of 4-homo-isotwistane-3-amine. It has thus been discovered that 8-exohydroxymethylendotri-cyclo- (5.2.1.02'6) -decane, or 5,6-endotriethyleneeneornornane-2-exo-methylol of formula (II) is produced by subjecting endodicyclo-pentadiene oxo reaction (reaction of an olefin with carbon monoxide and hydrogen), in the presence of a rhodium catalyst; the product obtained is then hydrogenated (Japanese Laid-open Application N ° 68167/1977).

The inventors have done a great deal of research on the compounds and derivatives of formula (II); they discovered that the ester and ether compounds of formula (I) have odoriferous properties, and are very useful in the composition of perfumes; their scent is very varied: smell of fruit, smell of green grass, smell of wood. This invention is based on these discoveries.

This invention provides original tricyclic ester and ether compounds of formula (I), having odoriferous properties.

The suitable substituents, represented by R in formula I, are: saturated alkyl groups of 1 to 5 carbon atoms, methyl, ethyl, propyl, isopropyl, butyl, sec.-butyl, tert.-butyl, amyl, isoamyl, sec.-amyl; unsaturated alkyl groups of 1 to 5 carbon atoms, allyl, buto-2-enyl groups; acyl groups of 1 to 5 carbon atoms, formyl, acetyl, propionyl, butylyl, iso-butylyl.

The synthesis of the compounds of formula (I) is characterized by usual esterification or etherification reactions. The synthesis of esters is characterized, for example, in that compounds of formula (II) are reacted with corresponding carboxylic acids, in the presence of a catalyst for esterification, such as a mineral acid. The synthesis of ethers is characterized in that the compounds of formula (II) are reacted with corresponding alkyl halides, in the presence of sodium hydride. Glycidyl ethers are produced by oxidizing allyl ethers with peracids, or other similar products.

The starting material is synthesized, 8-exohydroxymethylendo-tricyclo- (5.2.1.02'6) -decane, by hydrolyzing 8- or 9-exoformyl-endotricyclo- (5.2.1.02> 6) -deca-3-ene presence of a hydrogenation catalyst. The hydrogenation reaction takes place at a temperature which varies between room temperature and 200 ° C., in an inert solvent such as a lower alcohol (methanol or ethanol), and an ether solvent such as ether. diethyl or tetrahydro-furan; 1/100000 to 1/100 mol of hydrogenation catalyst are added per mole of olefin aldehyde. Raney nickel or platinum oxide is used as the hydrogenation catalyst.

The synthesis of 8- or 9-exoformylendotricyclo- (5.2.1.02> 6) -deca-3-ene is characterized in that one reacts with endodicyclopentadiene (endotricyclo- (5.2.1.02-6) -deca-3 , 8-diene) with carbon monoxide and hydrogen, in the presence of a rhodium / triarylphosphine catalyst (cf. “Synthetic Communication”, 6.199 (1976) and Japanese Laid-open Application N ° 68167/1977, already cited).

The rhodium / triarylphosphine catalysts which can be used are represented by the formulas:

HRh (CO) (PR3) 3 XRh (CO) (PR3) 2 XRh (PR3) 3

where R is phenyl or a phenyl group substituted by an alkyl or alkoxy radical; X is a halogen chosen from chlorine, bromine, iodine. A catalyst can be used, in an adequate amount, from 0.01 to 1% relative to the endodicyclopentadiene. The oxo reaction preferably takes place in an inert solvent, for example a hydrocarbon solvent, such as benzene or toluene, or in an ether solvent: ethyl ether or tetrahydrofuran; the reaction pressure is 20 to 150 atm, and at a temperature of 50 to 150 ° C.

The following carboxylic acids are used for the synthesis of the ester compounds of formula (I): formic acid, acetic acid, propionic acid, butyric acid, isobutyric acid. In the synthesis of ethers, the following alkyl halides are used: methyl iodide, ethyl iodide, n-propyl iodide, iodide

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isopropyl, butyl iodide, sec.-butyl iodide, tert.-butyl iodide, amyl iodide, isoamyl iodide, sec.-amyl iodide, allyl iodide, buto-2- iodide enyl, alkyl bromides and alkyl chlorides. The following peracids are used for the synthesis of glycidyl ether compounds: peracetic acid, perbenzoic acid, m-chloroperbenzoic acid, p-nitroperbenzoic acid and monoperoxyphthalic acid.

The compounds of formula (I) are original and have odoriferous properties, described above.

According to the Japanese Laid-open Application No. 70036/1977, the 8-hydroxymethyltricyclo- (5.2.1.02'6) -decane substituted on the tri-methylene bridge, in positions 3- 4- and 5-, as well as its ester and ether, also have odoriferous properties. However, these compounds are different from the compounds of the invention. It should be noted that the conformation in space of the tri-methylene and hydroxymethyl groups of the compounds described in the publications cited above is not yet known; these compounds are therefore obtained in the form of a mixture of the various isomers.

Furthermore, the compounds prepared according to this invention each have a unique structure, in which the trimethylene and hydroxymethyl groups are substituted respectively on the exo and endo side. Consequently, the compounds of this invention always have the same scent linked to changes in the ratio of the isomers present, which is not the case with the usual odoriferous compounds.

The compounds of formula (I) of this invention have a pleasant and defined odor, varying from the smell of green grass to the smell of fruit and wood; they can therefore be used in the composition of perfumed products such as soaps, shampoos, cosmetics, waxes of superior quality.

The following examples are detailed illustrations of this invention. The invention is not however limited to these examples.

Example 1:

Preparation of 8-exohydroxymethylendotricyclo- (5.2.1.02'6) -decane

149.6 g (0.9 mol) of a mixture of 8- and 9-exoformylendotricyclo- (5.2.1.02-6) -deca-3-ene, 100 ml of metha-nol and 200 mg are placed in an autoclave platinum oxide. The air in the autoclave is replaced by hydrogen gas; the mixture is stirred at room temperature under hydrogen gas pressure of 90 atm, until all the hydrogen is absorbed. The temperature is raised to 120 ° C, so that the rest of the hydrogen is absorbed. After cooling, the catalyst is filtered, and the solvent is removed from the filtrate under reduced pressure. A colorless oily product is obtained.

Elementary analysis for Ci iHlaO:

Calculated: C 79.2 H 10.5%

Found: C 79.5 H 10.9%

Boiling point: 95-96 ° C / 0.3 mmHq Tlfê = 1.5129

IR (net): cm ~> 3600-3100 (OH), 1470.1450.1020 (CO) NMR (CDCI3 as solvent, internal standard TMS): 4.3 (OH), 3.3 (-CH20, doublet, J = 7 Hz), 2.5-0.9 (15H, multiplet), 166 (1.9, M +), 148 (13), 135 (100), 107 (13), 93 (16), 91 ( 13), 81 (19), 80 (22), 79 (28), 67 (47), 41 (12)

Example 2:

Preparation of endotricyclo- (5.2.1.02-6) -deca-8-exo-ylmethyl-formate

3.0 g of 8-exohydroxymethylendotricyclo- (5.2.1.02,6) -decane are dissolved in 30 ml of formic acid. 1 ml of concentrated sulfuric acid is added dropwise to this solution, with constant stirring. This solution is stirred for 3 h at room temperature; the mixture is then diluted with 100 ml of ethyl ether, then washed twice with 100 ml parts of water, and once with a 10% sodium carbonate solution. The ethereal layer is

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dried, concentrated; the residue is subjected to fractional distillation; 3.0 g of the desired methylformate are obtained (yield = 86%).

Elementary analysis for C12H1802:

Calculated: C 74.19 H 9.34%

Found: C 74.43 H 9.20%

Boiling point: 116-118 ° C / 8 mmHq $ 11 = 1.4964

IR: 1730 cm-1.1 180 cm-1

The compound has a woody odor when used in scented compositions.

Example 3:

Preparation of endotricyclo- (5.2.1.02-6) -déca-8-exo-yImethyl-acetate

The same process is followed as that described in Example 1, but replacing the formic acid with acetic acid; 3.34 g of the desired methyl acetate are thus obtained (yield = 89%).

Elementary analysis for C13H20O2:

Calculated: C 74.96 H 9.68%

Found: C 74.88 H 9.27%

Boiling point: 66-68 ° C / 0.15 mmHg Tl $ = 1.4910

IR: 1743 cm-1.1240 cm-1

The compound has a wood odor, usable in perfumed compositions.

Example 4:

Preparation of 8-exomethoxymethylendotricyclo- (5.2.1.02-6) -decane

A mixture of 10 ml of xylene and 0.96 g of sodium hydride (0.02 mol, oily 50%) is refluxed; 3.0 g (0.018 mol) of 8-exohydroxymethylendotricyclo- (5.2.1.02-6) -decane dissolved in 50 ml of xylene are added dropwise. After reflux for 15 min, 2.84 g (0.02 mol) of methyl iodide is added; the mixture is refluxed for 1 h. After cooling to room temperature, the excess sodium hydride is filtered. 100 ml of ethyl ether are then added to the filtrate; the mixture is washed with a concentrated sodium chloride solution. The etherole layer is dried, concentrated; the residue is subjected to fractional distillation. 2.60 g of the desired product are obtained. Yield = 80%.

Elementary analysis for Ci2H20O:

Calculated: C 79.94 H 11.18%

Found: C 80.08 H 11.16%

Boiling point: 79-80 ° C / 2 mmHg

= 1.4931 IR: 1115 cm- '

The compound has a woody odor in the scented compositions.

Example 5:

Preparation of 8-exoethoxymethylendotricyclo- (5.2.1.02> 6) -decane

The same process is used as that described in Example 3,

but the methyl iodide is replaced by 3.13 g (0.02 mol) of ethyl iodide. 2.73 g of the desired product are obtained. Yield = 78%.

Elementary analysis for C13H22O:

Calculated: C 80.35 H 11.41%

Found: C 80.18 H 11.57%

Boiling point: 77-78 ° C / l, 5 mmHg

= 1.4873 IR: 1115cm-1

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The compound has a green wood odor in the scent compositions.

Example 6:

Preparation of 8-exo-n-propyloxymethylendotricyclo- (5.2.1.02-6) -decane

The same process is used as that described in Example 3, but the methyl iodide is replaced by 3.4 g (0.02 mol) of n-propyl iodide. 2.89 g of desired product are obtained. Yield = 77%.

Elementary analysis for C14H24O:

Calculated: C 80.71 H 11.61%

Found: C 80.78 H 11.41%

Boiling point: 80 ° C / 1 mmHg $ 11 = 1.4850 IR: 1115cm- '

The compound has a green grass odor in the scent compositions.

Example 7:

Preparation of 8-exoallyloxymethylendotricyclo- (5.2.1.02> 6) -decane

The same process is used as that described in Example 3, but the methyl iodide is replaced by 3.36 g (0.02 mol) of allyl iodide. 2.97 g of the desired product are obtained. Yield = 80%.

Elementary analysis for C14H220:

Calculated: C 81.50 H 10.75%

Found: C 81.73 H 10.68%

Boiling point: 107-108 ° C / 3 mmHg il $ = 1.4974 IR: 1100 cm-1

The compound has a flower scent, between the smell of green grass and the smell of wood, in the scented compositions.

Example 8:

Preparation of endotricyclo- (5.2.1.02'6) -dêca-8-exo-ylmethyl-10 glycidylether

1.2 g (5.8 mol) of allyl ether, obtained according to the method described in Example 7, are dissolved in chloroform. 0.96 g of m-chloroperbenzoic acid dissolved in 50 ml of chloroform is added dropwise. This addition lasts 30 min at biante friends temperature. The solution is stirred for 30 min. When the reaction is complete, the mixture is washed with a solution of sodium carbonate, then with a solution of sodium chloride; the organic layer is dried. Excess chloroform is removed by distillation under reduced pressure. The residue is subjected to fractional distillation. 1.12 g of the desired product are obtained. Yield = 87%.

Elementary analysis for C14H2202:

Calculated: C 75.63 H 9.97%

Found: C 75.89 H 9.83%

25 Boiling point: 118 ° C / 3 mmHg il $ = 1.5011 IR: 1100, 760 cm- '

The compound has a woody odor in perfumed compositions.

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Claims (6)

637,359 2. An 8-exohydroxymethylendotricyclo- (5.2.1.02'6) -decane derivative according to claim 1, wherein R is a saturated or unsaturated alkyl group of 1 to 5 carbon atoms. 2 CLAIMS 1. Derivative of 8-exohydroxymethylendotricyclo- (5.2.1.02> 6) -decane of formula (I): 10 3. 8-Exohydroxymethylendotricyclo- (5.2.1.02'6) -decane derivative according to claim 2, wherein R is a saturated alkyl group of 1 to 4. The 8-exohydroxymethylendotricyclo- (5.2.1.02-6) -decane derivative according to claim 2, wherein R is an unsaturated alkyl group from 1 to 5. An 8-exohydroxymethylendotricyclo- (5.2.1.02'6) -decane derivative according to claim 1, wherein R is an acyl group of 1 to 5 carbon atoms. 5 carbon atoms. 5 carbon atoms. 5 where R represents a saturated or unsaturated alkyl group of 1 to 5 carbon atoms, an acyl group of 1 to 5 carbon atoms or a glycidyl group, and a group ROH2C— at position 8 of a norbornane ring, on the side exo. 6. 8-Exohydroxymethylendotricyclo- (5.2.1.02'6) -decane derivative according to claim 1, wherein R is a glycidyl group.