CH658646A5 - BICYCLE DERIVATIVES (2.2.1) HEPTANE, PROCEDURE FOR THEIR PREPARATION AND PERFUME COMPOSITIONS CONTAINING THEM. - Google Patents

Description

The present invention relates to new fragrant compounds, compositions containing said compounds and processes for preparing said compounds.

The present invention relates to new bicyclo- [2.2.1] heptane derivatives with a strong fragrance and more particularly it concerns bicycle [2.2.1] heptane derivatives represented by the general formula (I)

20

25

said process comprising the hydrogenation of 2-ethyl-den-5 (or 6) -hydroxymethylbicycle [2.2.1] heptane represented by the following formula (Ib):

(THE)

hoh2c

(Ib)

in the presence of a metallic catalyst.

14. Process for preparing 2-ethyl-5 (or 6) -formylbicyclo- [2.2.1] heptane according to claim 2, represented by the following formula (Id):

where R represents a formyl group or a hydro-simethyl group connected in position 5 or 6 and the dotted line 35 represents a single bond or a double bond.

The present invention also relates to perfume compositions containing the compounds with formula (I) and the processes for preparing the compounds themselves.

The inventors synthesized various compounds and evaluated their usefulness. The 2-ethylidenbicycle compound [2.2.1] heptene (hereinafter referred to as EBH) which is easily obtained, can be used as a starting material for the preparation of the compounds of the present invention. EBH is represented by the following formula (II):

ohc

(Id)

said process comprising the reaction of 2-ethyliden-5 (or 6) -formylbicycle [2.2.1] heptane represented by the following formula (la)

ohc

(there)

with hydrogen in the presence of a hydrogenation catalyst.

15. A perfume composition comprising a derivative according to claim 2 in an amount such as to impart a fragrance to the composition and an acceptable excipient or diluent.

(II)

It has been discovered that new compounds, derived from EBH, represented by the fomula (I) have an excellent 60 and strong fragrance.

The compounds 2-ethyliden-5 (or 6) -formylbicycle [2.2.1] heptane (la) and 2-ethyl-5 (or 6) -formylbicycle [2.2.1] heptane (Id) in the formula (I), in wherein R represents a formyl group, have a strong green-floral fragrance and that 2-ethyliden-5 (or 6) -hydroxymethyl-65 cycle [2.2.1] heptane (Ib) and 2-ethyl-5 (or 6) - hydroxymethylbicycle [2.2.1] -heptane (le) in the formula [I]; in which R represents a hydroxymethyl group, they have a strong green aromatic-floral fragrance.

4

Accordingly, the compounds (I) of the present invention, alone or mixed with other perfume components, can be used in products that require the addition of refugee, such as perfumes, cosmetics, soaps, detergents, shampoos, ce-5 re, room fresheners and the like.

When the compound (I) is used in a perfume composition it can be used alone or in a mixture with other components of the perfume composition. The compound (I) is usually present in an effective fragrant quantity, in 10 kinds from 0.01 to 50% by weight, preferably from 0.1 to 25% by weight, more preferably from 0.5 to 15% by weight. The other ingredients in the perfume composition may comprise organic solvents such as alcohols, ketones, aldehydes and esters. The perfume composition typically contains 15 long chain alcohols and various fragrant oils of natural origin and additional fragrant compounds.

When the compound (I) is used in cosmetic compositions, it is present in an effective fragrant quantity, usually from 0.1 to 10% by weight, preferably from 0.1 to 5% UCJ 20 jn by weight. a cosmetic excipient suitable for application to human skin as a powder, cream or lotion, together with other ingredients, constitutes the remainder of the composition.

When the compound (I) is used in a soap, detergent or shampoo, it is present in an effective fragrant quantity, usually from 0.01 to 10% by weight, preferably from 0.01 to (Id) 5% by weight. The remaining part of the composition is made up of conventional soaps, detergents, etc.

30 It is readily apparent that compound (I) can be used in a variety of compositions other than those listed above.

The compound of the present invention can for example be prepared according to the following reaction scheme.

H2

catalyst RH

} OHC

CO / H2

oHc-crn catalyst I l I

metallic

(Id)

metallic idixiro

That is, 2-ethylene-5 (or 6) formylbicycle [2.2.1] heptane (la) can be prepared by reaction of EBH (II) with carbon monoxide and hydrogen gas in the presence of a rhodium catalyst and 60 therefore 2-ethyliden -5 (or 6) -hydroxymethylbicycle [2.2.1] heptane (Ib) can be prepared by reaction of the compound (la) with metal hydride and furthermore 2-ethyl-5 (or 6) -hydroxymethylbicycle [2.2.1] heptane ( le) can be prepared by reaction of the compound (Ib) with gaseous hydrogen in the presence of a metallic catalyst. 65 2-ethyl-5 (or 6) -formicIbicic [2.2.1] heptane (Id) can be prepared by hydrogenation of the compound (la) in the presence of a metallic catalyst.

EBH hydroforming is known as evidenced by the short

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U.S. vector No. 3,894,985. However, the process described in U.S. Pat. No. 3 894 985 relates to a method for the preparation of a diformyl compound represented by the following formula (III):

cho

Thus the hydroformylation of both the double bonds of EBH takes place and therefore this reference does not concern a method for the preparation of monoformyl compounds such as those of the present invention.

The process for preparing the compounds of the present invention is discussed below in greater detail.

In the present description the pressure values are indicated using the "atmosphere" and "millimeters of mercury" units. To transform these values into «Pascal» (unit of measurement adopted by the International System) it is necessary to multiply the values expressed in atmospheres by the coefficient 98066.5 and those expressed in millimeters of mercury by the coefficient 133.322.

Preparation of the compound (la):

The rhodium catalysts used in the reaction of the present invention contain rhodium halides, rhodium oxides, rhodium carboxylates, rhodium nitrates or rhodium complexes having a binder such as phosphine, amine, olefin, carbon monoxide, hydrogen and the like. RI1X3 (where X is halogen), RI12O3, [Rh (OCOCH3)] 2, Rh (N03) 3, Rh6 (CO) 6, [RhX (CO) 2] 2, can be mentioned as specific examples of these rhodium catalysts. RhX3 (CsH5N) 3, [RhX (C8Hi2)] 2, Rh (acac) 3 (acac = acetyl acetate-born), Rh (PR '3) 3 where R represents an aromatic group containing 6-12 carbon atoms RhX ( CO) - (PR '3) 2, RhH (CO) (PR' 3) 3 and the like. Among these catalysts, RhH (CO) (PR '3) 3 is particularly useful. These rhodium compounds are usually used as homogeneous catalysts but can also incidentally be used as heterogeneous catalysts for depositing the catalyst on a solid and porous support, such as activated carbon, alumina, silica and the like.

The catalyst is used in quantities of 1 X IO-1 to 1 X IO-6 moles, per mole of EBH and preferably from 1 x IO "2 to 1 X IO-5 moles per mole of EBH.

By adding 1-100 moles of tertiary phosphine per mole of the catalyst, various advantages can be realized such as the inhibition of the decomposition of the catalyst and the reduction of the reaction pressure.

The reaction temperature varies from the ambient temperature (about 20 ° C) to 150 ° C and preferably from 50 ° C to 130 ° C. The mixing pressure ratio of the carbon monoxide gas with respect to the hydrogen gas varies from 0.5 to 2.0 and preferably from 0.8 to 1.2. The reaction pressure varies from 1 atmosphere to 200 atmospheres and preferably from 20 atmospheres to 150 atmospheres.

Reaction solvents comprising hydrocarbons such as hexane, heptane, benzene, toluene, xylene and the like and esters such as tetrahydrofuran, dioxane and the like are used. However, the reaction can also be carried out in the absence of a reaction solvent. In the process of the present invention it is essential to block the reaction at the time in which both carbon monoxide and hydrogen are consumed in an amount of 0.1-1.3 moles and particularly in the preferred form in the amount of 0.1-1 , 1 moles per mole of EBH.

When carbon monoxide and hydrogen are consumed in quantities greater than 1.1 moles per mole of EBH in the reaction, the formation of the diformyl compound as a by-product begins and the yield of the desired monoformyl product decreases. On the other hand, when the reaction is carried out with conversions of less than 0.1 moles, in order to increase the selectivity of the desired monoformyl compound, using an amount of less than 0.1 moles, the reaction allows only a low yield over time and is uneconomical.

The following data demonstrate that the products obtained as indicated above have a structure represented by formula (la). That is, in 'H-NMR of EBH, the absorption of the two types of olefinic protons is observed and the peaks correspond to those that appear at S = about 5.20 (complicated multiplet, IH) and 8 = about 5.85 (multiplet relatively simple, 2H) respectively. In view of the relationship of their respective areas, the absorption of the first is due to the olefinic proton of one vinylidene group and the absorption of the other is due to the orbinene proton of the norbornene type.

On the other hand, in the H-NMR of the product of the present invention, the peak of the hydrogen of the formyl group appears at y = 9.48 (singlet, IH). However, the olefin proton peak at y = about 5.25 disappears and only a olefin proton peak at y = about 5.25 appears (complicated multiplet, IH).

Accordingly, it has been found that the product of the present reaction has a chemical structure as represented by the formula (la) in which a formyl group is introduced into the orbine of the norbornene type, but not the ethylidene group.

In the process for the preparation of 2-ethyliden-5 (or 6) -formylbicycle [2.2.1] heptane, in order to further increase the yield, it is preferable to use a large excess of tertiary phosphine with respect to the quantity of the rhodium compound.

This improved process is a process for the preparation of 2-ethyliden-5 (or 6) -formylbicycle [2.2.1] heptane which causes an oxo reaction of EBH in the presence of a catalyst consisting of a rhodium compound and a phosphine tertiary, which is characterized in that said rhodium compound is used in quantities of 0.1 to 100 ppm (in terms of metallic rhodium) based on the amount of 2-ethylidenbicycle [2.2.1] -heptane and said tertiary phosphine is used in quantities of 200 to 10000 times, preferably from 1000 to 10000 times the quantity in moles of the rhodium compound.

In general, these tertiary phosphines are used as promoters to increase selectivity, but they also have an effect or activity of unfavorably lowering the reaction rate. For this reason it has been considered that the quantity of phosphine to be added should be in the range of 10 to 100 times the quantity in moles of the rhodium compound. However, when an oxo reaction for EBH was carried out in the presence of a rhodium catalyst containing a tertiary phosphine added to it (in quantities from 1 to 100 moles, considered a preferred quantity), the selectivity (yield) was at most equal to about 70%.

Studies on the reaction conditions for the oxo reaction of EBH have been conducted and it has been unexpectedly found that when the tertiary phosphine is used in much higher quantities than had been conventionally considered, the yield of 2-ethyliden-5 (or 6) -formylbicycle [2.2.1] heptane exceeds 90% with a very small amount of the rhodium compound.

The rhodium compounds useful in the improved process are rhodium-phosphine complexes such as RhH (CO) (PRiR2R3) 3, RhCl (CO) (PRiR2R3) 2 and RhCl (PRiR2R3) 3 in which Ri, R2 and R3 are equal or different groups and they are each alkyl, cycloalkyl or an aryl group which can be replaced with an alkoxy or alkyl group having from 1 to 6 carbon atoms. In this case the rhodium compounds are used in quantities of 0.1 to 100 ppm (in terms of metallic rhodium) on the basis of the EBH quantity. Very good yields can be obtained at low con-

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centering, in particular from 1 to 10 ppm (in terms of metallic rhodium) based on the amount of EBH.

The tertiary phosphines useful according to the present invention are those represented by formula (III):

R

1

R

2

R

3

where Ri, R.2 and R3 are as previously defined.

Examples of phosphines are triethylphosphine, tripropylphosphine, tribu-tylphosphine, tricyclohexylphosphine, dioctylphenylphosphine, triphenylphosphine, ditolylphenylphosphine, methoxyphenyphiphenylphosphine, trismethoxyphenylphosphine, and. Triphenylphosphine is particularly preferred.

It is necessary to use these tertiary phosphines in quantities of 200 to 10000 times, preferably from 1000 to 10000 times the molar amount of the rhodium compound. When the quantity of tertiary phosphine is lower than the lower limit indicated above, high-boiling by-products are formed which unfavorably reduce the yield.

The reaction can be carried out in a solvent. However, the desired products can be obtained with high yields without using any solvent, as will be shown in the following examples. Therefore it is not always necessary to conduct the reaction in a solvent.

The reaction temperature varies according to the quantity of catalyst, since the reaction rate varies according to the quantity of catalyst. When a very small amount of catalyst is used, a high reaction temperature is required. When a relatively high amount of catalyst is used, it is necessary to lower the reaction temperature in order to avoid heat generation due to the rapid reaction. Preferably the reaction is carried out at a temperature in the range of 80 to 180 ° C, particularly from 100 to 150 ° C.

The pressure at which the reaction is conducted is in the range of 20 to 250 atmospheres. The mixing ratio of the carbon monoxide gas with respect to the hydrogen gas is in the range of 0.5 to 2.0, preferably 0.8 to 1.2.

The improved process for the preparation of 2-ethyl-den-5 (or 6) -formylbicycle [2.2.1] heptane has the following advantages.

(1) EFBH can be obtained with high yields and with a small amount of the rhodium catalyst.

(2) The side reaction that converts EBH, which is a diolefin, to a dialdehyde, is inhibited in the presence of an excess amount of tertiary phosphine. The reaction is substantially blocked at a stage in which only the double bond in the EBH position 5 has reacted. Therefore the reaction can be easily controlled.

(3) The amount of products resulting from side reactions is decreased. After recovering EFBH by distillation, the residue containing the catalyst can be reused in the oxo reaction.

It is surprising that the selectivity (yield) is increased by reducing the amount of catalyst, while the amount of added tertiary phosphine is kept constant. Thus it is clear that the improved process is superior to the conventional ones.

Preparation of the compound (Ib)

Aluminum lithium hydride, sodium boron hydride and the like are used as exemplary metal hydrides. This reaction is carried out in accordance with the general reduction process, for example under the conditions described by L.F. Fieser and M. Fieser "Reagents for Organic Synthesis" John Wiley and Sons, Inc., New York (1967).

Preparation of the compound (s):

This hydrogenation is carried out according to the general catalytic reduction processes using a metallic catalyst such as Raney nickel, platinum dioxide, palladium / carbon, ruthenium / carbon and the like.

In this case it is particularly preferred to carry out this reaction at a hydrogen pressure in the range of 10 to 150 atmospheres and at a reaction temperature of 30 to 150 ° C.

Preparation of the compound (Id):

In this hydrogenation in which the compound (la) is iodine-generated to obtain the compound (Id), solid catalysts such as nickel Raney, platinum dioxide, palladium / carbon, ruthenium / carbon and the like and homogeneous catalysts such as RhXPR are used as exemplary catalysts '(where X represents a halogen atom and R' represents an aromatic group containing 6-12 carbon atoms) and the like.

In the case of the use of solid catalysts, the compound (le) is produced as a by-product due to the reduction of the formyl group of the compound (la). Therefore it is preferable to use PhCl (PPh3) 3 particularly in order to obtain only the highly pure compound (Id).

In this reaction, to obtain the compound (Id) by hydrogenation of the compound (la), it is preferable to carry out the reaction at a hydrogen pressure in the range of 10 to 150 atmospheres and at a reaction temperature of 30-150 ° C.

The following examples further illustrate the present invention.

Example I

225 g (1.88 moles) of EBH, 2 g (2.2 mmoles) of tris (triphenylphospine) rhodium chloride and 1 g of triphenylphosphine were loaded into a 500 ml autoclave and the air in the autoclave was replaced with carbon monoxide.

The autoclave was pressurized up to 80 atmospheres with carbon monoxide at a partial pressure of 40 atmospheres and with hydrogen at a partial pressure of 40 atmospheres and the reaction mixture was stirred at 80 ° C. When 1.88 moles of carbon monoxide and 1.88 moles of hydrogen were consumed (the amount of consumption was measured by a pressure meter), the autoclave was cooled and the pressure was reduced to atmospheric pressure and in content was removed . The reaction products were distilled under reduced pressure to obtain 2-ethyliden-5 (or 6) -formylbicycle [2.2.1] heptane. The purified compound had a very strong floral green odor.

Boiling point: 96 - 97 ° C / 16 mmHg Yield: 184 g (65.2% yield)

Elemental analysis: (like CioHuO)

calculated (%): C 79.96; H 9.39 format (%): C 79.81; H 9.50 IR (pure, cm- '): 3050, 2810, 2710, 1720, 1690' H-NMR (solvent CDCI3, internal reference TMS): 9.48 (IH, —CHO)

5.25 (complicated multiplet IH, = CH-CH3) 3.3-1.2 (complicated multiplet, 12H)

MS (relative intensity):

There were at least 4 isomers of this compound.

The results of the GC / MS measurements of the product using

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spheres with CO at a partial pressure of 20 atmospheres and with H2 at a partial pressure of 20 atmospheres and then heated to 100 ° C. After reaching the required temperature, the autoclave was further pressurized to 100 atmospheres (initial pressure with CO and H2 with the same partial pressures. When the pressure was lowered to a measured pressure of 40 atmospheres or less, the autoclave was still pressurized at 100 atmospheres with CO and H2 with the same partial pressures. The reaction was completed at the time when the gas absorption ceased. The reaction required approximately 3.5 hours.

The autoclave was cooled to ordinary temperature. The pressure was brought to atmospheric pressure. The content was removed and distilled under reduced pressure to give 2-ethyliden-5 (or 6) -formylbicycle [2.2.l] heptane.

Boiling point: 96-97 ° C / 16 mm of mercury

Yield: 141.8 g (94.4% of the theoretical yield), residual 6.6 g.

Example 4

6.6 g of the residue obtained in Example 1 and 120 g (1 mole) of EBH were loaded into an autoclave. The reaction was carried out similarly to that of Example 1 to give 140.6 g (93.6% yield) of EFBH.

By the process of the present invention, the desired product can be obtained with high yields as illustrated in Example 1 and therefore smaller quantities of by-products are formed. Therefore EFBH can be produced with high yields even when the catalyst in the residue is reused.

TABLE 1

tertiary rhodium phosphine catalyst

quantity (mg)

concentration (ppm)

concentration in terms of metallic Rh (ppm)

solvent quantity (mg)

molar ratio towards the catalyst rhesus

Reaction temp. (° C)

Reaction time (hr)

conversion (%)

selectivity (%)

Surrender (%)

Example

3

10

83.3

9.33

-

2.86

1000

110

3.5

100

94.4

94.4

5

1

8.33

0,933

-

2.86

10000

140

2.3

100

90.5

90.5

6

100

833

93.3

-

28.6

1000

100

2.5

100

88.1

88.1

Comparative example

1

100

833

93.3

0

0

100

1.5

92.0

28.5

26.2

2

100

833

93.3

toluene

0

0

100

2.0

100

32.8

32.8

3

100

833

93.3

-

0,286

10

100

1.0

100

50.1

50.1

4

100

833

9.33

-

2.86

100

100

2.0

100

71.1

71.1

5

10

83.3

9.33

-

0,286

100

110

3.5

90.6

80.9

73.3

Note: 1. The starting material is 120 g (one mole) of EBH 3. Tertiary phosphine: PPI13

2. Rhodium compound: [RhH (CO) (PPh3) 3] 4. CO / H2 = 1 (initial pressure: 100 atmospheres).

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Example 7

3.7 g (0.1 moles) of liter aluminum hydride and 50 ml of di- ether

a capillary column (column length 40 m, Thermon 600 T, product of K.K. Shimazu Seisakusho) are as follows:

Peak 1 (9%): 150 (M +, 13), 122 (7), 121 (10), 106 (6), 94 (28),

93 (100), 91 (25), 79 (26), 77 (22), 55 (5) 5

Peak 2 (35%) 150 (M +, 12), 122 (8), 121 (9), 106 (6), 94 (29), 93 (100), 91 (25), 79 (24), 77 ( 22), 55 (7)

Peak 3 (50%) 150 (M +, 53), 121 (45), 106 (20), 94 (29),

93 (100), 92 (16), 91 (50), 79 (54), 77 (36), 55 (15) 10

Peak 4 (6%) 150 (M +, 33), 121 (20), 106 (20), 94 (56),

93 (100), 92 (14), 91 (52), 79 (56), 77 (44), 67 (13).

Example 2 15

225 g (1.88 moles) of EBH, 2 g (2.2 mmoles) of triphenylphosphine) -carbonyl rhodium hydride, 1 g of triphenylphosphine and 250 mml of benzene were loaded into an autoclave of 11. This reaction was carried out in the same conditions of Example 1 to obtain 206.2 g of 2-ethyliden-5 (or 6) -formylbicycle [2.2.1] heptane (yield 20 73.0%).

Example 3

102 g (1 mole) of EBH, 10 mg (1.09 x 10 — s moles) of [RhH (CO) (PPH3) 3] and 2.86 g (1.09 x IO-2 moles) of triphenylphosphi- 25 na were loaded into an autoclave. Then the autoclave air was replaced with nitrogen, the autoclave was pressurized to 40 atmospheres Examples 5 and 6

The tests were conducted by loading the quantities of rhodium and tertiary phosphine compounds to produce EFBH. The yield and selectivity, including the results of Example 1 and comparative examples, are shown in Table 1 above.

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anhydrous ethyl were stirred in a 4-necked flask, with a capacity of 200 ml, at room temperature. A mixture consisting of 15 g (0.1 mol) of 2-ethylidene-5 (0 6) -formylbicycle [2.2.1] heptane obtained in Example 1 and 50 ml of anhydrous diethyl ether was slowly added dropwise. After completion of the addition, the mixture was kept under reflux for an additional 1 hour and then cooled to room temperature. 3.7 ml of water, 3.7 ml of 15% aqueous caustic soda solution and then 11 ml of water in the order indicated were added and as a result an aluminum compound precipitated. The precipitate was filtered by a glass filter and then washed thoroughly with diethyl ether. Then the organic layer was thoroughly washed with saturated aqueous solution of common salt and dried on anhydrous magnesium sulfate.

After filtration the solvent was evaporated and still distilled under reduced pressure to give 2-etiiden-5 (or 6) -hydroxymethylIbi-cycle [2.2.1] heptane. This compound had a strong green floral aromatic odor.

Boiling point: 60-62 ° C / 15 mm of mercury Yield: 14.8 g (97.4% yield)

Elemental analysis: (like This HjgO)

calculated (%): C 78.90; H 10.59 found (%): C 79.41; H 10.32 IR (pure, cm-1): 3600-3100 (wide absorption) 3050, 1690, 1030

'H-NMR (CDCI3 solvent, internal TMS reference): 5.3 (complicated multiplet, IH, = CH-CH3)

3.35 (doublet, 2H, -CH2-OH)

3.0-0.8 (complicated multiplet, 13H)

MS (relative intensity):

152 (M +, 40) 121 (34), 119 (22), 105 (18), 94 (27), 93 (100), 91 (35), 79 (60), 77 (27).

Example 8

5 g (32.8 mmoles) of 2-ethyliden-5 (or 6) -hydroxymethylbicyclo- [2.2.1] heptane obtained in Example 3, 500 mg of 5% ball-diatal coal and 50 ml of ethanol were loaded in a 100 ml autoclave and stirred at 100 ° C under a pressure of 50 atmospheres of hydrogen. By the time the absorption of hydrogen gas ceased, the autoclave was cooled to room temperature and the hydrogen pressure was reduced to atmospheric pressure. The content was taken. After filtering the catalyst, the solvent was evaporated and distilled under reduced pressure to obtain 2-ethyl-5 (or 6) -hydroxymethylbicycle [2.2.1] heptane. This compound had a strong green aromatic odor.

Boiling point: 49-50 ° C / 0.09 mm of mercury Yield: 4.8 g (yield 94.9%)

Elementary analysis: how (CioHisO)

calculated (%): C 77.87; H 11.76 found (%): C 77.59; H 11.83 IR (pure, cm- '): 3600-3100 (wide absorption) 1040, 1020' H-NMR (CDCI3 solvent, internal reference TMS): 3.40 (doublet, 2H, -CH2-OH)

3.30 (singlet, IH, -OH)

2.35-0.4 (complicated multiplet, 15H)

MS (relative intensity):

154 (M +, 0.4), 124 (10), 123 (100), 107 (9), 95 (16), 81 (67), 80 (12), 79 (19), 67 (63), 55 (19).

Example 9

30 g (0.2 moles) of 2-ethyliden-5 (or 6) -formyl bicyclo [2.2.1] -heptane obtained in Example 1, 20 ml of benzene and 190 mg (0.2 mmoles) of RhCl ( PPh3) 3 were loaded into a 100 ml autoclave and the reaction was carried out at 100 ° C and at the pressure of 90 atmospheres of hydrogen. By the time the absorption of hydrogen gas ceased, the autoclave was cooled to room temperature and the hydrogen pressure was reduced to atmospheric pressure. The content was taken. Then the solvent was evaporated and distilled under reduced pressure to obtain 2-ethyl-5 (or 6) - formylbicycle [2.2. l] heptane.

This compound had a strong green aromatic odor.

Yield: 25.1 g (Yield 82.4%)

Boiling point: 95-98 ° C / 17 mm of mercury

Elementary analysis:

calculated (%): C 78.90; H 10.59 found (%): C 78.52; H 10.71 'H-NMR (CDCI3 solvent, internal TMS reference): 9.65 (IH, -OH)

2.8-0.5 (complicated multiplet, 15H)

MS (relative intensity):

152 (M +, 1), 123 (57), 108 (20), 95 (55), 81 (90), 79 (18), 67 (100), 66 (19), 55 (29), 41 (39 ).

Example 10

Composition of perfume of the pink type:

geraniol 130 (g)

citronellol 70

phenylethyl alcohol 593

nerolo 50

geranium oil 20

palmarosa oil 20

benzyl acetate 20

hydroxycitronellal 40

linalool 25

octanol 1

octyl aldehyde 1

geranyl acetate 10

1000

A new perfume composition having a fresh rose smell was obtained by adding 20 g of 2-ethyliden-5 (or 6) - formylbicycle [2.2.1] heptane to the perfume composition described above (1000 g).

Example 11 Composition of perfume for shampoo:

linalool 50 (g)

jasmine oil 20

phenyl ethyl alcohol 150

rhodinol 150

rose oil 10

hydroxycrystalline 300

indole 2 4- (4-hydroxy-4-methylphenyl) -3-

-cyclohexen-1-carboxyaldehyde 75

a-hexylcinnamic aldehyde 150

Cyclamic aldehyde 40

sandalwood oil 50

phenylacetaldehyde 3

1000

A new perfume composition having a fresh lily of the valley smell was obtained by adding 100 g of

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2-ethyliden-5 (or 6) -hydroxymethylbicycle [2.2.1] heptane to the perfume composition reported above (1000 g).

Example 12 Composition of perfume for co- water

Ionia:

lemon oil

350 (g)

bergamot oil

300

orange oil

150

bigarade peptigrain oil

100

bigarade neroli oil

20

lavender oil

70

sandalwood oil

10

I

Example 13

Flower-type perfume composition of the lime tree:

hydroxycitronellal 180 (g)

linalool 180

a-ionone 100 aldehyde p-ter-butyl-a-methyl-

hydrocinnamic 100

phenyl ethyl alcohol 100

hexyl salicylate 50

linalyl anthranilate 50

galbanum oil 2

Roman chamomile oil 1

Eugenol 5

coumarin 5

dipropylene glycol. 227

1000

1000

A new perfume composition having a pleasant fresh odor for cologne was obtained by adding 50 g of 2-ethyl-5 (or 6) -hydroxymethylbicycle [2.2.1] heptane to the perfume composition reported above (1000 g).

Perfume composition having an energetic and more natural odor like the flowers of the lime tree was obtained by adding 2 g of 2-ethyl-5 (or 6) -formylbicycle [2.2.1] heptane to the perfume composition 25 indicated above (1000 g).

v

Claims (13)

658 646 "1. R, (III) where Ri, R2 and R3, which are the same or different, are an alkyl group, a cycloalkyl group, an aryl group, or a group 35 aryl substituted with an alkyl or alkoxy group from C 1 to C 3, the quantity of said rhodium compound is used in quantities from 200 to 10000 times by moles. 2. Bicycle derivative [2.2.1] heptane according to claim 1, characterized in that said derivative is 2-ethyliden-5 (or 6) -formylbicycle [2.2. l] heptane. 2 CLAIMS 1. Bicycle derivatives [2.2.1] heptane with formula (I): which includes reacting the 2-ethylidenbicycle [2.2.1] heptene, represented by the formula (II) (THE) (II) wherein R represents a formyl group or a hydroxymethyl group connected in position 5 or in position 6 and the dotted line represents a single bond or a double bond. 3 658 646 (there) 16. A cosmetic composition comprising a derivative according to claim 2 in an amount such as to impart a fragrance to the composition and an acceptable excipient or diluent. 17. A soap, detergent or shampoo composition comprising a derivative according to claim 2 in an amount such as to impart a fragrance to the composition and an acceptable excipient or diluent. with a metal hydride. Bicycle derivative [2.2.1] heptane according to claim 1, characterized in that said derivative is 2-ethyliden-5 (or 6) -hydroxymethylbicycle [2.2.1] heptane. 4 ohc (there) which includes reacting 2-ethylidenbicic [2.2.1] heptene represented by the following general formula (II) (II) with 0.1 to 1.3 moles of carbon monoxide and with 0.1 to 1.3 moles of hydrogen, in the presence of a rhodium catalyst. Bicycle derivative [2.2.1] heptane according to claim 1, characterized in that said derivative is 2-ethyl-5 (or 6) -hydroxymethylbicycle [2.2.1] heptane. 5. Bicycle derivative [2.2.1] heptane according to claim 1, characterized in that said derivative is 2-ethyl-5 (or 6) -formylbicycle [2.2.1] heptane. 6. Process for preparing 2-ethyliden-5 (or 6) -formylbicycle [2.2.1] heptane according to claim 2, represented by the following general formula (la): 7. Process for preparing 2-ethylene-5 (or 6) -formylbicycle [2.2.1] heptane according to claim 2, represented by formula (la): ohc (there) with carbon monoxide and with hydrogen in the presence of a catalyst of a rhodium compound and of a tertiary phosphine, characterized in that said rhodium compound is used in quantities from 0.1 to 100 ppm in terms of metallic rhodium on the basis of the amount of 2-ethylidenbicycle [2.2.1] heptene and called tertiary phosphine, which is represented by the formula (III): 20 8. Process according to claim 7, characterized in that said tertiary phosphine is used in quantity 40 from 1000 to 10,000 mol times the amount of rhodium catalyst. 9. Process according to claim 7, characterized in that said rhodium catalyst is a catalyst having the formula RhH (CO) (PRiR2R3) 3, RhC (CO) (PRiR2R3) 2 or 45 RhC (PRiR2R3) 3j where Ri, R2 and R3 are equal or different groups and are each an alkyl, cycloalkyl, aryl or aryl group substituted with alkyl or alkoxy from Ci to Ce. 10. Process according to claim 7, characterized in that said tertiary phosphine is triphenylphosphine. 50 11. Process according to claim 7, characterized in that said reaction is carried out in the absence of solvent. 12. Process for preparing 2-ethylene-5 (or 6) -hydroxime-tilbicycle [2.2.1] heptane according to claim 2, represents 55 to by the following general formula (Ib): HOH2C (Ib) said process comprising reacting 2-ethyliden-5 (or 6) -formylbicycle [2.2.1] heptane represented by the following formula (la) 13. Process for preparing 2-ethyl-5 (or 6) -hydroxymethyl-bicyclo [2.2.1] heptane according to claim 2, represented by the following formula (s): H0H2C (the)