FR2528035A1 - NOVEL DERIVATIVES OF BICYCLO (2.2.1) HEPTANE, PROCESS FOR THEIR PREPARATION AND THEIR USE FOR THE PREPARATION OF SCENTED COMPOSITIONS - Google Patents

Abstract

There are described highly aromatic, or highly scented, compounds of the following formula in which R denotes a formyl group or a hydroxymethyl group which is bonded in the 5- or 6-position, and the broken line denotes a single bond or double bond. There are furthermore described compositions which comprise the compound I, and processes for the preparation of the compounds I.

Description

 The present invention relates to novel scented compounds, compositions containing these compounds and methods for preparing such compounds.

dans laquelle R représente un groupe formyle ou un groupe hydroxyméthyle fixé en position 5- ou 6- et la ligne en pointillé représente une simple liaison ou une double liaison. Cette invention concerne également des compositions de parfums contenant les composés de formule (I) et des procédés pour la préparation de ces composés.This invention relates to novel bicyclo L2.2.13 heptane derivatives having a strong fragrance and more particularly to bicyclo r 2-2.1-] heptane derivatives represented by the general formula (I)

wherein R represents a formyl group or a hydroxymethyl group attached at 5- or 6- position and the dotted line represents a single bond or a double bond. This invention also relates to perfume compositions containing the compounds of formula (I) and processes for the preparation of these compounds.

 The Applicant has synthesized various compounds and estimated their utilities.

The easily obtainable 2-ethylidenebicyclo [2.2.1) heptene (hereinafter referred to as EBH) may be used as a starting material for the preparation of the compounds of the present invention. EBH is represented by the following formula (II)

 New compounds derived from E.B.H. and represented by the formula (I) possess an excellent and excellent fragrance.

The compounds 2-ethylidene-5 (or 6) -formylbicyclo C2.2.1] heptane (1a) and 2-ethyl-5 (or 6) -formylbicyclo E2.2.i3 heptane (Td) of formula (I), in where R represents a formyl group, have a strong green plant fragrance, and 2-ethylidene-5 (or 6) -hydroxymethylbicyclo 2.2.1] heptane (Tb) and 2-ethyl -5 (or 6) -hydroxymethylbicyclo t2 .2.1 3 heptane (Ic) of formula (I), in which R represents a hydroxymethyl group, possess a strong fresh and spicy fragrance of Fleur.

 Therefore, the compound (I) of this invention, alone or in admixture with other scented compounds, can be used in products requiring the addition of perfumes such as perfumes, cosmetics, soaps, detergents, shampoos, waxes, products for cooling the atmosphere and the like.

When the compound (I) is used in a perfume composition, it may be used alone or in admixture with other compounds for perfume compositions. Compound (I) will generally be present in an effective amount for perfuming, generally from about 0.1 to about 50% by weight, preferably about 0.1 to about 25% by weight, more preferably about 0.5 to about 15% by weight. The other ingredients in the scented composition may include organic solvents such as alcohols, ketones, aldehydes and esters. The scented composition will generally contain
long chain alcohols and various fragrance oils of natural origin and various additional scented compounds.

 When the compound (I) is used in cosmetics, it is present in an amount sufficient to perfume, generally 0.01 to 10% by weight, preferably 0.1 to 5% by weight. A cosmetic carrier suitable for application to human skin such as a powder, cream or lotion with other ingredients forms the remainder of the composition.

 When the compound (I) is used in a soap, detergent or shampoo, it is present in an effective amount, generally 0.01 to 10% by weight, preferably 0.01 to 5% by weight. The rest of the composition consists of conventional soaps, detergents, etc.

 It will be clear that it is possible to use the compound (I) in a wide variety of compositions other than those described above.

The compound of this invention can be prepared for example according to

<tb><SEP> scheme of <SEP> reaction <SEP> shown <SEP> below.
<Tb>

<SEP> H2
<tb><SEP> cat1ysur <SEP> 0HC
<tb><SEP> hpstallic
<tb><SEP> I <Id)
<tb><SEP> Catalyst <SEP> of <SEP> n <SEP> h
<tb><SEP>)<SEP> 0HC
<tb><SEP><11)<SEP> co / H2 <SEP> \ hYdride <SEP> mettalic
<tb><SEP>)<SEP> HOH2C <SEP> c <SEP> ata <HOH2C <SEP> H0H2C
<tb><SEP> (Ib) <SEP> (the)
<Tb>
2-Ethylidene-5 (or 6) formylbicyclo C2.2.1] heptane (ira) can be prepared by reacting EBH (II) with carbon monoxide and hydrogen gas in the presence of a rhodium catalyst, and then 2-ethylidene-5 (or 6) hydroxymethylbicyclo [2.2.1] heptane (Db) by reacting the compound (la) with a metal hydride, and then-2-ethyl-5 (or 6) hydroxymethylbicyclo [2.2. 1] heptane (Ic) by reacting the compound (Ib) with hydrogen gas in the presence of a metal catalyst, 2-ethyl-5 (or 6-formylbicyclo [2.2.1] heptane (I d ) by hydrogenating the compound ta) in the presence of a metal catalyst.

The hydroformylation of EBH is known as that is demonstrated in US Patent 3,894,985. However, the method described in the patent
No. 3,894,985 relates to a method for preparing a diformyl compound represented by the following formula (III)

Thus, the hydroformylation of the two double bonds of
EBH and accordingly this reference does not relate to 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 in more detail below
Preparation of the compound (I a):
The rhodium catalyst used in the reaction of this invention contains rhodium halides, rhodium oxides, rhodium carboxylates, rhodium nitrates, or rhodium complexes having a ligand such as phosphine, amine, olefin, carbon monoxide. , hydrogen and the like. As specific examples of these rhodium catalysts, mention may be made of RhX3 (where X is a halogen), Rh2O3, [Rh (OCOCH3) 2] 2, Rh (NO3) 3,
Rh6 (CO) 6, [RhX (CO) 2] 2, RhX, (C5H5N) 3, [RhX (C8H12)] 2, Rh (acac) 3 (acac = acetylacetonate), Rh (PR'3) 3 where wherein R 'is an aromatic group containing 6-12 carbon atoms, RhX (CO) - (PR'3) 2, RhH (CO) (PR'3) 3 and the like. Among these catalysts, Rh H (CO) (PR 3) 3 is particularly useful These rhodium catalysts are generally used as a homogeneous but inci deent catalyst they can be used as a heterogeneous catalyst by depositing the catalyst on a porous solid support such as only silica, alumina, activated charcoal and the like.

The catalyst is used in an amount of 1x10 1 to 1 × 10 -6 moles per mole of EBH, and preferably 1 × 10 -2 to 1 × 10 5 moles per mole of
EBH.

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

 The reaction temperature is from room temperature (about 20 C) to 1500C, and preferably from 50 C to 1300C. The ratio of the mixing pressure of the carbon monoxide gas to the hydrogen gas is from 0.5 to 2.0 and preferably from 0.8 to 1.2. The reaction pressure is from 1 atmosphere to 200 atm and preferably from 20 atmospheres to 150 atm.

 Reaction solvents including hydrocarbons such as hexane, heptane, benzene, toluene, xylene and the like are used and ethers such as tetrahydrofuran, dioxane and the like. However, it is possible to carry out the reaction in the absence of a reaction solvent.

 In the process of the present invention, it is essential to stop the reaction at a time when both carbon monoxide and hydrogen are consumed in an amount of 0.1 - 1.3 moles, and in particular preferably 0.1 - 1.1 moles per mole of EBH.

 When in the reaction the carbon monoxide and hydrogen are consumed in excess of the amount of 1.1 moles per mole of EBH, the diformyl compound begins to be produced as a by-product and the yield of monoformyl product desired decreases. On the other hand, when the reaction proceeds with a lesser conversion below 0.1 mole in order to increase the selectivity to the desired monoformyl compound, using an amount below 0.1 mole, the reaction gives a low yield per unit of time and it is not economical.

 The following data demonstrate that the products obtained above have a structure represented by the formula (Ia). However, in the 1H-NMR of EBH, we observe the absorption of two types of olefinic protons, and the corresponding peaks appear at # = close to 5.20 (complicated multiplet, 1H) and at # = close to 5.80 (relatively simple multiplet, 2H) respectively. In view of the proportion of their respective surfaces, the absorption of the first is due to the olefinic proton of a vinylidene group and the absorption of the latter is due to the olefinic proton norbornene type.

 Moreover, in the 1 H-NMR of the product of this reaction, the peak of the hydrogen of the formyl group appears at i = 9.48 (singlet, 1H). However, the peak of the olefinic proton at i = near 5.85 disappears and only an olefinic proton peak at # near 5.25 <complicated multiplet, 1H) appears.

 As a result, it is found that the product of this reaction has a chemical structure represented by the formula # a), in which a formyl group is introduced into the norbornene type olefin but not into the ethylidene group.

 In the process for the preparation of 2-ethylidene-5 (or 6) formylbicyclo [2.2.2] heptane, in order to further increase the yield, it is preferred to use a large excess of tertiary phosphine in relation to the amount of the rhodium compound.

This improved process is a process for preparing 2-ethylidene 5 (or 6) -formylbicyclo E 2.2.1 3 heptane by performing an oxo reaction of
EBH in the presence of a rhodium and tertiary phosphine compound catalyst, which is characterized in that the rhodium compound is used in an amount of 0.1 to 100 ppm (expressed as rhodium metal) by relative to the amount of 2-ethylidene -bicyclo L2.2.1 3 heptane and in that the tertiary phosphine is used in an amount of 200 to 10,000 times, preferably 1000 to 10,000 times molar, that of the rhodium compound.

 In general, these tertiary phosphines are used as a promoter to increase the selectivity but they also have an effect or activity to adversely decrease the rate of reaction. For this reason, it was considered that the amount of phosphine to be added should be 10 to 100 times molar that of the rhodium compound. However, when an oxo-reaction for EBH is carried out in the presence of a rhodium catalyst containing a tertiary phosphine added thereto (in an amount of 1 to 100 times in mole considered as a preferred amount), the selectivity (yield) is about 70% at best.

 Reaction conditions for the oxo-EBH reaction have been investigated and it has been unexpectedly found that when the tertiary phosphine is used in a much larger amount than is conventionally considered, the yield of 2-ethylidene-5 (or 6) -formylbicyclo L2.2.1 3 heptane exceeds 90% with a very small amount of rhodium compound.

The rhodium compounds useful in the improved process are rhodium-phosphine complexes such as RhH (CO) (PR1R2R3) 3, RhC1 (CO) (PR1R2R3) 2 and RhC1 (PR1R2R3) 3 where R1, R2 and R3 are identical groups or each different being an alkyl, cycloalkyl or aryl group which may be substituted by an alkoxy or alkyl group having 1 to 6 carbon atoms. In this case, the rhodium compounds are used in an amount of 0.1 to 100 ppm (expressed as rhodium metal) relative to the amount of EBH. Very good yields can be obtained at a low concentration, in particular from 1 to 10 ppm (expressed as rhodium metal) relative to the amount of
EBH.

dans laquelle R1, R2 et R3 sont tels que définis ci-dessus.Tertiary phosphines useful in the present invention are those represented by the formula (III)
(III)

wherein R1, R2 and R3 are as defined above.

 Examples of phosphines are triethylphosphine, tripropylphosphine, tributylphosphine, tricyclohexylphosphine, dioctylphenylphosphine, triphenylphosphine, ditolylphenylphosphine, methoxyphenyldiphenylphosphine, trismethoxyphenylphosphine and tritolylphosphine.

Triphenylphosphine is particularly preferred.

 It is necessary to use these tertiary phosphines in an amount of from 200 to 10,000 times, preferably from 1000 to 10,000 times, by mole that of the rhodium compound. When the amount of tertiary phosphine is below the lower limit above, high boiling by-products are formed which adversely affect the yield.

 The reaction can be carried out in a solvent. However, the desired products can be obtained in high yields without the use of any of the solvents mentioned in the following examples. Therefore, it is not always necessary to carry out the reaction in a solvent.

 The temperature of the reaction varies with the amount of catalyst since the reaction rate varies depending on the amount of the catalyst. When a small amount of catalyst is used, a high reaction temperature is required. When a relatively large amount of catalysts is used, it is necessary to lower the temperature of the reaction to avoid heat generation due to rapid reaction. Preferably, the reaction is carried out at a temperature in the range of 80 to 1800C, in particular 100 to 1500C.

 The pressure at which the reaction is carried out is from 20 to 250 atmospheres. The ratio of carbon monoxide gas to hydrogen gas is 0.5 to 2.0, preferably 0.8 to 1.2.

 The improved process for the preparation of 2-ethylidene-5 (or 6) -formylbicyclo2.2.1 heptane has the following advantages.

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

 (2) a secondary conversion reaction of EBH, which is a diolefin, to a dialdehyde is inhibited in the presence of an excess amount of the tertiary phosphine. The reaction is essentially stopped at a stage where only the double bond at the 5 position of EBH has reacted. So, we can easily control the reaction.

 (3) the quantities of the products resulting from the side reactions are reduced. After recovery of EFBH by distillation, a residue containing the catalyst can be reused in the oxo reaction.

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

Preparation of the compound (Ib)
As the exemplary metal hydride, aluminum hydride, lithium hydride, sodium hydride, boron hydride and the like are used, which reaction is carried out according to the general reduction method, for example under the described conditions.
LF Pieser and M. Fieser "Reagents for Organic Synthesis" John Wiley and
Sounds Inc, New York (1967).

Preparation of the compound (ic)
This hydrogenation is carried out in accordance with general methods of catalytic reduction using a metal catalyst such as Raney nickel, platinum dioxide, palladium / coal, ruthenium coal and the like.

 In this case, it is more particularly preferred to carry out this reaction under a hydrogen pressure of from 10 to 150 atmospheres and at a reaction temperature of 30 to 150.degree.

Preparation of the compound (Id)
In the hydrogenation, or the compound (fa) is hydrogenated to obtain the compound (Id), solid catalysts such as Raney nickel, platinum dioxide, palladium / charcoal, ruthenium are used as examples of catalysts. charcoal and the like and homogeneous catalysts such as RhXPR '(where X represents a halogen atom and R' represents an aromatic group containing from 6 to 12 carbon atoms) and the like. In the case of using solid catalysts, compound c) is obtained as by-products due to the reduction of the formyl group of compound a). So we prefer to use
PhCl (PPh3) 3 in particular to obtain only the compound (@d) of high purity.

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

 The following examples illustrate the present invention.

Example 1
225 g (1.88 mol) of EBH are introduced into a 500 ml autoclave.
2 g (2.2 gnole) of tris (triphenylphosphine) rhodium chloride and 1 g of triphenylphosphine and the air was replaced in the autoclave with carbon monoxide. The autoclave at 80 atmospheres with carbon monoxide at a partial pressure of 40 atmospheres and with hydrogen at a partial pressure of 40 atmospheres is pre-purified and the reaction mixture is stirred at 80 ° C.

When 1.88 moles of carbon monoxide and 1.88 moles of hydrogen were consumed (the amount consumed was measured by a pressure measuring device), the autoclave was cooled, the pressure was reduced to the pressure atmospheric and we remove the contents. The products of the reaction are distilled under reduced pressure to give 2-ethylidene -5 (or 6) -formylbicyclo [2.2.1] heptane. The purified compound has a very strong strong smell
flower.

Boiling point: 96-97 C / 16 mmHg
Yield: 184 g (65.2% yield)
Elemental analysis: (for C10 H140)
Calculated: (%): C = 79.96: H = 9.39
Found (%): C = 79.81: H = 9.50
IR (neat, om: 3050, 2810, 2710, 1720, 1690
1H NMR (CDCl3 solvent, TMS internal reference)
9.48 (1H, -CHO)
5.25 (complicated multiplet 1H, = CH-CH3)
3.3 - 1.2 (complicated multiplet, 12H)
SM (relative intensity)
There are at least 4 isomers for this compound. The results of the measurement GC / MS of the product using a capillary column (column length 40 meters, Thermon 600 T, a product of KKShimazu 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)
Peak 2 (35X) 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)
Peak 4 (6X) 150 (M +, 33), 121 (20),
106 (20), 94 (56), 93 (100),
92 (14), 91 (52), 79 (56),
77 (44), 67 (13)
Example 2
225 g (1.88 mol) of EBH, 2 g (2.2 mol) of tris (triphenylphosphine) hydrido carbonyl rhodium, 1 g of triphenylphosphine and 250 ml of benzene are introduced into a 1-liter autoclave. reaction under the same conditions as in Example 1 to obtain 206.2 g of 2-ethylidene (or 6) -formylbicyclo [2.2.1] heptane (yield 73.0%).

Example 3
102 g (mole) of EBH, 10 mg (1.09 X mole) of ERhH (CO) (PPH3) 3) and 2.86 g (1.09 X 10 10 mole) of triphenylphosphine were charged into an autoclave. . After replacing the air in the autoclave with nitrogen, the autoclave is pressurized at 40 atmospheres with CO at a partial pressure of 20 atmospheres and with H2 at a partial pressure of 20 atmospheres, and then heated to 1100C. After reaching the required temperature, the autoclave is again compressed to 100 atmospheres (initial pressure) with CO and H2 at the same partial pressures. When the pressure decreases to a pressure of 40 atmospheres or less, the autoclave is pressurized to 100 atmospheres with CO and H 2 at the same partial pressures. The reaction is completed when the gas absorption is complete. The reaction requires about 3.5 hours.

 The autoclave is cooled to an ordinary temperature. The pressure is brought back to atmospheric pressure. The contents are removed and distilled under reduced pressure to give the desired 2-ethylidene-5 (or 66-formylbicyclo [2.2.1] heptane.

Boiling point: 96 - 97 C / 16 mmHg
Yield: 141.8 g (94.4% of theoretical yield), residue 6.6 g.

EXAMPLE 4
6.6 g of the residue obtained in Example 1 and 120 g (1 mole) of EBH are introduced into an autoclave. The reaction was conducted in a manner similar to that of Example 1 to obtain 140.6 g (93.6% yield) of EFBH.

 By the process of the present invention, the desired product can be obtained in high yields as shown in Example 1 and then a smaller amount of by-products is formed. Thus, EFBH can be produced in high yields even when the catalyst is reused in the residue.

Examples 5 and 6
Experiments were performed by varying the amounts of the 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 below.

Example 7
3.7 g (0.1 mol) of lithium aluminum hydride and 50 ml of anhydrous diethyl ether are stirred in a 200 ml 4-neck flask at room temperature. A mixture consisting of 15 g (0.1 mol) of 2-ethylidene-5 (or 6) -formylbicyclo 2.2.1 heptane obtained in Example 1 and 50 ml of diethyl ether is slowly added dropwise thereto. anhydrous. After completion of the addition, the mixture is further refluxed for 1 hour and then cooled to room temperature. 3.7 ml of water, 3.7 ml of a 15% aqueous sodium hydroxide solution and 11 ml of water are added in the order and as a result an aluminum compound precipitates. The precipitate is filtered off on a glass filter and then washed thoroughly with diethyl ether. Then the organic layer is vigorously washed with a saturated aqueous solution of common salt and dried with anhydrous magnesium sulfate.

 After filtration, the solvent is removed by evaporation and then distilled under reduced pressure to give 2-ethylidene -5 (or 6) -hydroxymethylbio2.2.1 heptane. This compound has a strong, fresh and spicy fragrance of Fleur.

Boiling point: 60 - 62 "C / 15 mmHg
Yield: 14.8 g (yield 97.4%)
Elemental analysis: (for C10 H16 O)
Calculated (X): C = 78.90: H = 10.59
Found (X): C = 79.41: H = 10.32
-1
IR (neat, cm): 3600 - 3100 (broad absorption) 3050, 1690,
1030
1 H-NMR (CDCl3 solvent, TMS internal reference)
5.3 (complicated multiplet, 1H, = CH-CH3)
3.35 (doublet, 2H, -CH 2 -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 mmol) of 2-ethylidene-5 (or 6) -hydroxymethylbicylo [2.2.1] heptane obtained in example 3, 500 mg of palladium / 5% charcoal are introduced into a 100 ml autoclave. and 50 ml of ethanol, and stirred at 1000C under a pressure of 50 atmospheres of hydrogen. When the absorption of the hydrogen gas stops, the autoclave is cooled to room temperature and the presence of hydrogen at atmospheric pressure is reduced. We remove the content. After removal of the catalyst by filtration, the solvent was removed by evaporation and distilled under reduced pressure to give 2-ethyl5 (or 6) -hydroxymethylbicyclo 2.2.1 heptane. This compound has a strong fresh and spicy fragrance.

Boiling point: 49 - 50 ° C / 0.09 mmHg
Yield: 4.8g (94.9% yield)
Elemental Ananlyse: (for C10H18O)
Calculated (X): C = 77.87: H = 11.76
Found (%): C = 77.59; H = 11.83
IR (neat, cm 1): 3600 - 3100 (broad absorption) 1040, 1020
1H-NMR (solvent CDCl3, internal standard TMS)
3.40 (doublet, 2H, - CH2-OH)
3.30 (singlet, 1H, -OH)
2.35 - 0.4 (complicated multiplet, 15H)
SM (relative intensity)
154 (H +, 0.4), 124 (10), 123 (100), 107 (9),
95 (16), 81 (67), 80 (12), 79 (19), 67 (63),
55 (19)
Example 9
An autoclave of 100 m1.30 g (0.2 mol) of 2-ethylidene 5 (or 6) -formylbicyclo [2.2.1 heptaneobtenu in example 1, 20 ml of benzene and 190 mg (0, 2 mmol of RhCl (PPh 3) 3 and the reaction is carried out at 100 ° C. under a pressure of 90 atmospheres of hydrogen When the absorbent of the hydrogen gas is complete, the autoclave is cooled to room temperature and the pressure of hydrogen at atmospheric pressure, the contents are removed, the solvent is removed by evaporation and distilled under reduced pressure to give 2-ethyl-5 (or 6) -formylbicyclo E2.2.1
heptane.

 This compound has a strong spicy fat fragrance.

Yield: 25.1 g (82.4% yield)
Boiling point: 95 - 98 C / 17mmHg
Elemental analysis
Calculated (%): C = 78.90: H = 10.59
Found (%): C = 78.52: H = 10.71
1 H - NMR (solvent CDCl3 internal reference TMS) TABLE 1

Catalysaur <SEP> of <SEP> rhochium <SEP> tertiary phomphine <SEP>
<tb> Conversion <SEP> Selectivity <SEP> Yield
<tb> Temperature <SEP> Time <SEP> of
<tb> Ouartité <SEP> Concentration <SEP> Corcoration <SEP> Qumtité <SEP> ratio <SEP> in <SEP> mole <SEP> of <SEP> reoction <SEP> reaction
<tb> ecorimed <SEP> in <SEP> Rh <SEP> Solvert <SEP> in <SEP> Catalyst
<tb> Rh <SEP> of <SEP> Rh
<tb> (mg) <SEP> (ppm) <SEP> (ppm) <SEP> (g) <SEP> (C) <SEP> (hr) <SEP> (%) <SEP> (%) <SEP > (%)
<tb> Example <SEP> 3 <SEP> 10 <SEP> 83.3 <SEP> 9.33 <SEP> - <SEP> 2.86 <SEP> 1000 <SEP> 110 <SEP> 3.5 <SEP > 100 <SEP> 94.4 <SEP> 94.4
<tb> Example <SEP> 5 <SEP> 1 <SEP> 8.33 <SEP> 0.933 <SEP> - <SEP> 2.86 <SEP> 1000 <SEP> 140 <SEP> 2.3 <SEP> 100 <SEP> 90.5 <SEP> 90.5
<tb> Example <SEP> 6 <SEP> 100 <SEP> 833 <SEP> 93.3 <SEP> - <SEP> 28.6 <SEP> 1000 <SEP> 100 <SEW> 2.5 <SEP> 100 <SEP> 88.1 <SEP> 88.1
<tb> Example
<tb> comparative <SEP> 1 <SEP> 100 <SEP> 833 <SEP> 93.3 <SEP> - <SEP> 0 <SEP> 0 <SEP> 100 <SEP> 1.5 <SE> 92.3 <SEP> 28.5 <SEP> 26.2
<tb>"<SEP> 2 <SEP> 100 <SEP> 833 <SEP> 93.3 <SEP> toluene <SEP> 0 <SEP> 0 <SEP> 100 <SEP> 2.0 <SEP> 100 <SEP > 32.8 <SEP> 32.8
<tb>'SEP> 3 <SEP> 100 <SEP> 833 <SEP> 93.3 <SEP> - <SEP> 0.286 <SEP> 10 <SEP> 100 <SEP> 1.0 <SEP> 100 <SEP > 50.1 <SEP> 50.1
<tb> 4 <SEP> 100 <SEP> 833 <SEP> 93.3 <SEP> - <SEP> 2.86 <SEP> 100 <SEP> 100 <SEP> 2.0 <SEP> 100 <SEP> 71 , 1 <SEP> 71.1
<tb>"<SEP> 5 <SEP> 10 <SEP> 83.3 <SEP> 9.33 <SEP> 0.286 <SEP> 100 <SEP> 110 <SEP> 3.5 <SEP> 90.6 <SEP > 80.9 <SEP> 73.3
<tb> (Note) 1. The starting material consists of 120 g (1 mole) of EBH 2. Rhodium compound: [RhH (CO) (PPh3) 3] 3. Tertiary Phosphine: PPh3 4. CO / H2 = 1 initial pressure: 100 atmospheres)
9.65 (1H, -OH-)
2.8 - 0.5 (complicated multiplet, 15 H)
SM (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
Scented composition having a scent similar to that of the rose
Geraniol 130 (g)
citronellol 70
phenylethyl alcohol 593
nerol 50
essence of geranium 20
palmarosa essence 20
benzyl acetate 20
hydroxy citronellal 40
linalol 25
octanol 1
octyl aldehyde 1
geranyl acetate 10
1000
A new perfume composition is obtained which has a fresh rose-like odor by adding 20 g of 2-ethylidene -5 (or 6) -formylbicyclo [2.2.1] heptane to the perfume composition obtained above (1000%). )
Example 11
Perfumed composition for shampoos
linalool 50 (g)
essence of jasmine 20
phenylethyl alcohol 150
rhodinol 150
essence of rose 10
hydroxy citronellal 300
indole 2
4- (4-hydroxy-4-methylpentyl) -3-cyclohexene-1-carboxy
aldehyde 75
aldehyde-hexylcinnamic 150
cyclamen aldehyde 40
sandalwood essence 50
phenyl acetaldehyde 3
1000
A new fragrance composition having a fresh cinder similar to that of lily of the valley is obtained by adding 100 g of 2-ethylidene -5 (or 6) -hydroxymethylbicyclo [2.2.1 heptane to the perfume composition obtained above (1000 g).

Example 12
Perfumed composition for cologne
lemon essence 350 (g)
bergamot essence 300
orange essence 150
petitgrain
essence of bigarade 100
essence of neroli bigarade20
lavender essence 70
sandalwood essence 10
1000
We obtain a new scented composition with a fresh
and sweet smell for cologne by adding 50 g of 2-ethyl-5 (or 6) hydroxymethylbicyclo [2.2.1 3 -heptane to the scented composition obtained above (1000g).

Example 13
Scented composition like linden blossom
hydroxycitronellal 180 (g)
linalool 180
-ionone 100
p-tert-butyl-methyl-aldehyde
hydrocinnamic 100
phenylethyl alcohol 100
hexyl salicylate 50
linalyl anthranilate 50
essence of galbanum 2
Roman chamomile oil 1
eugenol 5
coumarin 5
dipropylene glycol 227
1000
A new scented composition is obtained with an odor similar to that of the more natural linden flower and sliced by adding 2 g of 2-ethyl
5 (or 6) -formylbicyclo [[2.2.1] heptane to the perfume composition obtained
above (1000 g).

Claims (18)

1. Derivatives of bicyclo L2.2.1 heptane of formula (I)  (I)

 wherein R represents a formyl group or a hydroxymethyl group attached at 5- or 6- position and the dotted line represents a single or double bond.  2. Derivative of bicyclo [2.2.1 u heptane according to claim 1 characterized in that said derivative is 2-ethylidene -5 (or 6) formylbicyclo (2.2.1 heptane.  3. Derived from bicyclo 2.2.1] heptane according to claim 1, characterized in that said derivative is 2-ethylidene-5 (or 6) hydroxymethylbicyclo 2.2.1) heptane.  4. Derived from bicyclo 2.2.1 heptane according to claim 1, characterized in that said derivative is 2-ethyl-5 (or 6) hydroxymethylbicyclo [2.2.1] heptane.  The bicyclo [2.2.1] heptane derivative according to claim 1, characterized in that said derivative is 2-ethyl-5 (or 6) formylbicyclo [2.2.1] heptane.  6. Process for the preparation of 2-ethylidene-5 (or 6) formylbicyclo [2.2.1] heptane represented by the following formula (Ia)

 characterized in that it comprises the reaction of 2-ethylidenebicyclo [2.2.1 heptane represented by the following formula (II)  (II)

 with 0.1 to 1.3 moles of carbon monoxide and 0.1 to 1.3 moles of hydrogen in the presence of a rhodium catalyst.  7. Process for the preparation of 2-ethylidene-5 (or 6) formylbicyclo2.2.1 heptane represented

 in which R 1, R 2 and K 3, which are the same or different, represent an alkyl, cycloalkyl, aryl or aryl group substituted with an alkoxy or a C 1 -C 6 alkyl, is used in an amount of 200 to 10,000 times in mole; rhodium compound.

 heptane, and in that the tertiary phosphine which is represented by the formula (III) ::  with carbon monoxide and hydrogen in the presence of a catalyst of a rhodium compound and a tertiary phosphine, characterized in that said rhodium compound is used in an amount of from 0.1 to 100 ppm expressed in rhodium metal relative to the amount of 2-ethylidenebicyclo C2.2.1

<tb> which comprises the reaction of 2-ethylidene-bicyclo E2.2.1 heptene represented by the formula (II) <tb> <SEP> 1 <tb> <SEP> (la) <tb> <SEP> 0HC <tb> <SEP> 5 <SEP> 3 <tb> by <SEP> the <SEP> formula <SEP> (la)  8. The method of claim 7, characterized in that the tertiary phosphine is used in an amount of 1000 to 10000 times molar that of the rhodium catalyst.  9. Process according to claim 7, characterized in that the rhodium catalyst is a catalyst having the formula RhH (CO) (PR1R2R3) 3, RhCl (CO) (PR1R2R3) 2 or RhCl (PR1 R2R3) 3, where R1, R2, R3 are the same or different groups and each represents an alkyl, cycloalkyl, aryl or aryl group substituted with an alkoxy or C1-C6 alkyl.  10. Process according to claim 7, characterized in that the tertiary phosphine is triphenyl phosphine.  11. The method of claim 7, characterized in that the reaction is carried out in the absence of a solvent.  12. Process for the preparation of 2-ethylidene-5 (or 6) hydroxymethylbicyclo [2.2.1] heptane represented by the following formula (Ib)

  which comprises reacting 2-ethylidene-5 (or 6) formylbicyclo [2.2.1] heptane represented by the following formula (Ta) with a hydride

<Tb> <tb> metallic. <tb> <SEP> (las <tb> <SEP> OHC <SEP> (Ia) <tb> <SEP> 5 <tb> <SEP> 4 13. Process for the preparation of 2-ethyl-5 (or 6) -hydroxymethylbicyclo (2.2.1 3 heptane represented by the formula (Ic)  (Ic)

<tb> which comprises hydrogenating 2-ethylidene-5 (or 6) -hydroxymethylbicyclo 2.2.1 heptane represented by the following formula (Ib) in the presence of a catalyst <tb> HOH2C <SEP> t <SEP> 12 <tb> <SEP> HOH2C <SEP> <tb> next <SEP>: <SEP> 4  with hydrogen in the presence of a hydrogenation catalyst.

 which comprises reacting 2-ethylidene-5 (or 6) -formylbicyclo [2.2.1] heptane represented by the following formula (Ta)

 14.Process for the preparation of 2-ethyl-5 (or 6) -formylbicyclo [2.2.1] heptane represented by the following formula (Td) <Tb> <tb> metallic. <SEP> 1 <tb> <SEP> (lob) <tb> HOH2C <SEP> 2 <tb> <SEP> 5 <SEP> 3 <tb> <SEP> 4  A composition comprising: a bicyclo C 2.2.1 heptane derivative represented by the general formula (I)

 (I) wherein R represents a formyl group or a hydroxymethyl group attached at 5- or 6- position and the dotted line represents a single bond or a double bond present in an amount which imparts a fragrance to the composition and a diluent or an acceptable medium.  16. Composition according to claim 15 characterized in that it is a perfume composition.  17. Composition according to claim 15, characterized in that it is a cosmetic composition.  18. Composition according to claim 15, characterized in that it is a soap, a detergent or a shampoo.