GB2093022A - Derivatives of cyclopropane carboxylic acid - Google Patents

Abstract

Compounds of formula (I): <IMAGE> (in which: either one of the groups R1 and R2 represents a radical -CHO, radical -COalk1 in which alk1 represents an alkyl radical containing from 1 to 8 carbon atoms. a radical CO2alk2 in which alk2 represents an alkyl radical containing from 1 to 8 carbon atoms or a radical -CN, and the other of the groups R1 and R2 represents a hydrogen atom, or R1 and R2, together with the carbon atom to which they are bonded, form a radical <IMAGE> in which X represents an oxygen atom, a sulphur atom or an imino group, connected by the carbon atom at position @ to the double bond of the vinyl substituent; and R represents either a straight or branched alkyl radical containing from 1 to 12 carbon atoms optionally substituted by a cycloalkyl or cycloalkenyl radical containing from 3 to 6 carbon atoms or by a hydrocarbon chain containing from 2 to 8 carbon atoms and optionally interrupted by an oxygen atom or a >C = O group, or a straight or branched alkenyl or alkynyl radical containing from 3 to 8 carbon atoms, or a cycloaliphatic radical containing from 3 to 12 carbon atoms optionally including one or more double bonds, said cycloaliphatic radical being optionally substituted by one or more alkyl radicals, or an optionally substituted aralkyl radical containing from 7 to 12 carbon atoms) in all possible isomeric forms, including mixtures thereof, provided that when either R1 or R2 represents a group CHO, COalk1, CO2alk2 or <IMAGE> the double bond of the vinyl substituent of the cyclopropane ring has the geometry E, generally have agreeable odours and may be useful in the preparation of perfumes, and other perfumed articles or substances. Methods of preparation and uses of the compounds are described.

Description

SPECIFICATION Derivatives of cyclopropane carboxylic acid The present invention relates to new derivatives of cyclopropane carboxylic acid substituted at position 3 by a substituted vinyl group, a process for preparing them, their use as perfuming agents and compositions containing them.

The invention accordingly provides, in a first aspect, compounds of formula (I):

(in which: either one of the groups R, and R2 represents a radical -CHO, a radical -COalk, in which alk, represents an alkyl radical containing from 1 to 8 carbon atoms, a radical CO2alk2 in which alk2 represents an alkyl radical containing from 1 to 8 carbon atoms or a radical -CN, and the other of the groups R, and R2 represents a hydrogen atom, or R1 and R2, together with the carbon atom to which they are bonded, form a radical

in which X represents an oxygen atom, a sulphur atom or an imino group, connected by the carbon atom at position (3) to the double bond of the vinyl substituent; and R represents either a straight or branched alkyl radical containing from 1 to 1 2 carbon atoms optionally substituted by a cycloalkyl or cycloalkenyl radical containing from 3 to 6 carbon atoms or by a hydrocarbon chain containing from 2 to 8 carbon atoms optionally interrupted by an oxygen atom or a > C = 0 group, ora straight or branched alkenyl or alkynyl radical containing from 3 to 8 carbon atoms, or a cycloaliphatic radical containing from 3 to 1 2 carbon atoms optionally including one or more double bonds, said cycloaliphatic radical being optionally substituted by one or more alkyl radicals, or an optionally substituted aralkyl radical containing from 7 to 1 2 carbon atoms) in all possible isomeric forms, including mixtures thereof, provided that when either R1 or R2 represents a group CHO, COalk, CO2alk2 or

the double bond of the vinyl substituent of the cyclopropane ring has the geometry E.

The compounds of formula (I) can exist in numerous possible isomeric forms; in fact, they possess asymmetric carbon atoms at both position 1 and at position 3 of the cyclopropane ring, there is also the possibility of one or more isomers arising in the group R and the compounds can also possess isomerism with respect to the double bond of the group at position 3 of the cyclopropane ring; however, processes known to date only permit valid preparation of the products of configuration E with respect to the said double bond, except for the products in which R, or R2 represents a radical CN. Subject to this proviso therefore, it will be understood that references herein to compounds of formula (I) include reference to such compounds in all possible isomeric forms.

Alk, and alk2 preferably represent methyl, ethyl, n-propyl or isopropyl radicals.

When R represents a straight or branched alkyl radical, this is preferably a methyl, ethyl, propyl, isopropyl, butyl, isobutyl or tert-butyl, n-pentyl, n-hexyl 2-methyl-pentyl, 2,3-dimethylbu tyl, n-heptyl, 2-methylhexyl, 2,2-dimethylpentyl, 3,3-dimethylpentyl, 3-ethylpentyl, n-octyl, 2,2dimethylhexyl, 3,3-dimethyl hexyl, 3-methyl 3-ethylpentyl, nonyl, 2,4-dimethylheptyl or n-decyl radical.

When R represents an alkyl radical substituted by a cycloalkyl or cycloalkenyl radical, this is preferably an alkyl radical substituted by a cyclopropyl, cyclopentyl, or cyclohexyl radical, or by a cyclopentenyl or cyclohexenyl radical.

When R represents an alkenyl radical, this is preferably a butenyl, isobutenyl or crotyl radical.

When R represents an alkynyl radical, this is preferably a propynyl or butynyl radical.

When R represents a cycloaliphatic radical, this may, for example, be a cycloalkyl radical, preferably a cyclopropyl, cyclopentyl, cyclohexyl, cycloheptyl or cyclooctyl radical.

When R represent a cycloaliphatic radical containing more than one double bond, it preferably contains two double bonds.

When R represents a cycloaliphatic radical substituted by one or more alkyl radical(s), it is preferably a cycloaliphatic radical substituted by one or more methyl, ethyl or n-propyl radical(s).

When R represents an aralkyl radical, it is preferably a benzyl or phenylethyl radical, optionally substituted at the ortho, meta or para position by one or more alkyl radicals containing from 1 to 4 carbon atoms by one or more alkoxy radicals containing from 1 to 4 carbon atoms such as, for example, a methoxy radical, by one or more halogen atoms such as, for example, a chlorine or fluorine atom, by a trifluoromethyl radical or by a combination of these various substituents.

Preferred compounds of the invention are those of formula (I) for which the cyclopropane moiety has the (1 R,trans) or (1 R,cis) structure.

Among the preferred compounds of the invention are the compounds in which R represents a straight or branched alkyl radical containing from 1 to 4 carbon atoms, those in which R represents a benzyl radical, those in which R1 or R2 represents a radical CHO, those in which R or R2 represents a radical COCH3 or CO2CH3, and those in which R, or R2 represents a radical CN.

Among the preferred compounds of the invention are those prepared in the specific Examples given hereinafter, and especially the following compounds: -ethyl (1 R,cis)-2, 2-dimethyl-3-(2-methoxycarbonyl-(E)-ethenyli-cycloprnpane carboxylate, -benzyl (1 R,cis)-2,2-dimethyl-3-[(E + Z)-2-cyanoethenyl]-cyclopropane carboxylate and -methyl (1 R,cis)-2, 2-d imethyl-3-[(E)(dihydro-2-oxo-3-(2 H )-thienylidene)methyl]-cyclopropane carboxylate.

The compounds of formula (I) show interesting organoleptic properties which may render them useful as perfuming agents.

The compounds of formula (I) generally have an agreeable odour, for example a floral, flowery, green, woody or spicy odour. The experimental part set out hereinafter will indicate more precisely the odours released by certain products of formula (I) (see Example 37).

Because of their interesting olfactory properties, the products of formula (I) can be used as odorant agents to prepare perfumed substances or articles.

Accordingly, the invention provides, in a further aspect, perfumed substances or perfumed articles containing at least one compound of formula (I), as hereinbefore defined, as a perfuming agent.

Such perfumed substances or perfumed articles may be for example actual perfumes, or odorant perfuming compositions which may themselves serve as bases for perfumes and other products.

Examples of other perfumed articles or substances in the preparation of which the compounds of formula (I) may be useful include articles or hygiene such as, for example, soaps, talcs, shampoos, dentifrices, bath salts, foam baths or bath oils, and deodorants, and cosmetic products such as, for example, creams, cleansing milks, lotions make-up, lipsticks and nail varnishes.

Examples of further perfumed articles or substances in the preparation of which the compounds of formula (I) may be useful include detergent products such as, for example, washing powders or liquids, cleaning materials such as waxes, and insecticides.

The compounds of formula (I) can contribute an olfactory property to products devoid of odour; they can also enhance, heighten or modify the odour of compositions which themselves have a given odour. In addition, like any product having a pleasant odour, they can be used to mask the unpleasant odour of a product. Perfumed articles and substances such as the perfumes, hygiene products, cosmetics, detergent products and cleaning materials mentioned above may be made up according to the techniques usual in the industries concerned. These techniques are extensively described in the specialized literature and it is unnecessary to give particular embodiments here.

The perfumed articles or substances such as those given above may contain, in addition to the products of formula (I), additives or diluents which may be for example supporting, modifying, fixing, preserving and stabilizing vehicles and other ingredients such as supports, solvents, dispersants and emulsifiers conventionally used in the industries concerned.

When the compounds of formula (I) are used in perfumery, other products well-known to perfumers can be added to the products of formula (I), for example natural products such as vetiver oil, cedar-wood oil, bergamot oil, pine-needle oil, citrus oil, jasmin or mandarin oil, or synthetic products such as aldehydes used currently in perfurmery such as hydroxycitronellal, ketones such as o:-ionone, phenol compounds such as eugonol, alcohols such as geraniol or lactones such as coumarin.

The amounts of products of formula (I) to be used in the preparation of perfumed articles or substances vary greatly depending upon the nature of the product selected, the use it is desired to make of it, the intensity of the odour which is sought as well as, of course, the nature and the composition of the other ingredients which are added to the product of formula (I).

For example 0.1 to 2% by weight of products of formula (I) can be used in the case of detergents.

In the case of perfumes, for example from 0.1 to 10% by weight of products of formula (I) can be used. When the products of formula (I) are used in the preparation of perfuming compositions to be used as a base for perfumes, up to 20% by weight of products of formula (I) can be used.

The compounds of formula (I) may be prepared for example by the following processes which form further aspects of the invention.

Esterification of an acid of formula (all):

in which R1 and R2 are as hereinbefore defined, or a functional derivative thereof with an alcohol of formula ROH, in which R is as hereinbefore defined, or a functional derivative thereof, whereby the desired compound of formula (I) is obtained.

The reference to a functional derivative of the acid of formula (II) means, for example, an acid chloride or an anhydride. The reference to a functional derivative of an alcohol means, for example, a derivative of formula:

The esterification reaction can be carried out advantageosly by reacting the acid of formula (II) with the alcohol of formula ROH in the presence of dicyclohexylcarbodiimide or dicycloisopropylcarbodiimide.

The compounds of formula (I) may also be prepared using the following processes, in which a compound of formula (III):

in which alk; and alk; represent alkyl radicals containing from 1 to 4 carbon atoms and R, and R2 are as hereinbefore defined, or a compound of formula (IV):

in which R, and R2 are as hereinbefore defined, is reacted with an aldehyde of formula (V):

in which R is as hereinbefore defined, to obtain the corresponding compound of formula (I), according to a Witting-type reaction.

The following examples illustrate the invention without, however, limiting it.

The structures of the compounds of the examples hereinafter have, in each case, been confirmed by carrying out NMR spectra in deuterochloroform.

Example 1: Methyl (1 R, trans) 2, 2-dimethyl 3-r(E) (2-formyl ethenyl)) cyclopropane carboxylate.

A solution containing 46.8 g of methyl (1 R,trans) 2,2-dimethyl 3-formyl cyclopropane carboxylate, 193.2 g of triphenyl 1 ,3-dioxolan-2-yl methyl phosphonium bromide and 750 cm3 of dimethylformamide is heated to ~75 C. A solution containing 17.1 g of lithium methylate in methanol is then introduced over two and a half hours. The solution obtained is kept under agitation for 5 hours at this temperature, then at rest for one night at ambient temperature. The solution is poured, under agitation, into a mixture of water and ice, and the whole is extracted with ethyl ether, washed with a saturated aqueous solution of sodium chloride and evaporated to dryness at 50 C under reduced pressure. The residue obtained is dissolved in a solution containing 750 cm3 of tetrahydrofuran and 750 cm3 of N hydrochloric acid.The whole is kept under agitation at ambient temperature for 3 hours and poured into water. The whole is extracted with ethyl ether and washed with a saturated solution of sodium bicarobonate, then with a saturated solution of sodium chloride. It is dried and brought to dryness. The dry extract is taken up with a mixture of petroleum ether (B.Pt. 60-80'C) and ethyl acetate (8:2). The insoluble matter is separated. The solvent is evaporated and the residue is chromatographed on silica, elution being carried out with the mixture of petroleum ether and ethyl acetate (8:2). 37.6 g of expected product are obtained.

n 2D8= 1.5018.

The triphenyl 1,3-dioxolan-2-yl methyl phosphonium bromide used at the start of Example 1 was prepared as follows: 180 g of 2-(bromoethyl) 1,3-dioxolane and 260 g of triphenyl phosphine are heated to 80 C for 36 hours. The whole is cooled and the product obtained is dissolved in methylene chloride and poured slowly on to 3000 cm3 of ethyl ether. After agitation, the whole is separated and made into a paste with ethyl ether and 359 g of product are obtained, M.Pt. = 206 C.

Example 2: Methyl(lR,trans) 2,2-dimethyl-3-[(E) 3-oxo l-butenyl] cyclopropane carboxylate.

A mixture containing 5 g of methyl (1 R,trans) 2,2-dimethyl 3-formyl cyclopropane carboxylate, 11.3 g of 2-oxo propyl triphenyl phosphonium and 50 cm3 fo dichlorethane is refluxed for 2 hours. It is allowed to return to ambient temperature and the solvents are eliminated by distillation under reduced pressure. 1 9 g of an oil are obtained, which is purified by making into a paste in ethyl ether. The insoluble matter formed is eliminated by filtration and the filtrate is concentrated. 5 g of an oil are obtained, which is chromatographed on silica, elution being carried out with a mixture of cyclohexane and ethyl acetate, 7:3. 4.46 g of the product sought are thus obtained.

(a] D= + 108 j2.5' (c = 0.6% benzene).

Example 3: Ethyl (lR,trans) 2,2-dimethyl 3-f(E) 3-oxo 1-1 butenyl] cyclopropane carboxylate.

2 cm3 of pyridine are added, at + 5 to + 10 C, to a mixture containing 2.9 g of (1 R,trans) 2,2-dimethyl 3-[(E) 3-oxo 1-butenyl] cyclopropane carboxylic acid chloride, 1 cm3 of ethyl alcohol and 25 cm3 of benzene. The reaction mixture is agitated for 20 minutes at + 5 C and for 2 hours at ambient temperature. The reaction mixture is poured into an N/6 iced aqueous solution of hydrochloric acid. The whole is extracted with ethyl ether, washed with water and dried, and concentrated at 40 C under pressure. 4.1 9 g of an oil are obtained, which is purified by chromatography on silica (eluant: cyclohexane and ethyl acetate, 7:3). 1.43 g of the product sought are thus obtained.

LaL = + 82 + 3" (c = 0.5% benzene).

Example 4: Isopropyl (1 R,trans) 2,2-dimethyl 3-r(E) 3-oxo 1-butenyl] cyclopropane carboxylate.

The reaction is carried out as in Example 3, starting with 2.9 g of (1 R,trans) 2,2-dimethyl 3 [(E) 3'-oxo 1 '-butenyl] cyclopropane carboxylic acid chloride and 1.15 cm3 of isopropyl alcohol.

1.46 g of the product sought are obtained.

[&alpha;}D = + 63.5 3 (c = 0.3% benzene).

Example 5: Tert-butyl (1R,trans) 2,2-dimethyl 3-f(E) 3-oxo 1-butenyl] cyclopropane carboxylate.

The reaction is carried out as in Example 3, starting with 2.9 g of (1 R,trans) 2,2-dimethyl 3 ((E) 3-oxo 1-butenyl] cyclopropane carboxylic acid chloride and 1.4 cm3 of tertbutyl alcohol.

1.43 g of the product sought are obtained.

[&alpha;]D = + 67 4 (c = 0.25% benzene).

Example 6: Isopropyl (1 R, cis) 2, 2-dimethyl 3-F(E) 3-oxo 1-butenyl cyclopropane carboxylate.

The reaction is carried out as in Example 3, starting with 6 g of (1 R,cis) 2,2-dimethyl 3((E) 3oxo 1-butenyl] cyclopropane carboxylic acid chloride and 2.7 cm3 of isopropyl alcohol. 1.96 g of product sought are obtained. [a]D - 39' 5 (6 = 0.2% benzene).

Example 7: Methyl (1R,trans) 2,2-dimethyl 3-[2-methoxy carbonyl fE) ethenyl] cyclopropane carboxylate.

20.3 cm3 of a chloromethylenic solution of diazo-methane titrating 0.5 mole/l are poured into a solution containing 2.011 g of (1 R,trans) 2,2-dimethyl 3-[2-methoxy carbonyl (E) ethenyl] cyclopropane carboxylic acid and 5 cm3 of methylene chloride. Once the addition is finished, the whole is agitated for 10 minutes at 20 C then the methylene chloride is distilled off under reduced pressure. 2. 1 95 g of an oil are obtained, which is chromatographed on silica, elution being carried out with a mixture of benzene and ethyl acetate (95:5). 1.16 g of the product sought are thus obtained. (aL = + 105 3 (c = 0.5% in CHC13).

Example 8: Isopropyl (1R,trans) 2,2-dimethyl 3-[2-methoxy carbonyl (E) ethenyl] cyclopropane carboxylate.

The reaction is carried out as in Example 3, starting with 2.7 g of (1 R,trans) 2,2dimethyl 3 [2-methoxy carbonyl (E) ethenyl] cyclopropane carboxylic acid chloride in benzene and 1 cm3 of isopropyl alcohol. 1.7 g of product sought are obtained.

Coil, = + 84 (c = 1.25% CHCl3).

Example 9: Ethyl(1R,trans) 2,2-dimethyl 3-[2-methoxy carbonyl (E) ethenyl] cyclopropane carboxylate.

The reaction is carried out as in Example 3, starting with 2.7 g of (1 R,trans) 2,2-dimethyl 3 [2-methoxy carbonyl (E) ethenyl] cyclopropane carboxylic acid chloride in 12.5 cm3 of benzene and 1 cm3 of ethanol. 1.31 g of product sought are obtained.

[&alpha;]D = + 93 1.5 (c = 1% CHCl3).

Example 10: Tert-butyl (1R,trans) 2,2-dimethyl 3-[2-methoxy carbonyl (E) ethenyl] cyclopropane carboxylate.

The reaction is carried out as in Example 3, starting with 2.7 g of (1 R,trans) 2,2-dimethyl 3 [2-methoxy carbonyl (E) ethenyl] cyclopropane carboxylic acid chloride in 12.5 cm3 of benzene and 1.23 cm3 of tertbutyl alcohol. 1.05 g of product sought, melting at 674C, are obtained.

[&alpha;]D = + 75.5 2 (c = 0.5% CHCl3).

Example 11: Benzyl (1 R, trans) 2,2-dimethyl 3-[2-methoxy carbonyl (E) ethenyl] cyclopropane carboxylate.

The reaction is carried out as in Example 3, starting with 1.35 cm3 of benzyl alcohol and 12.5 cm3 of solution containing 1 mole/litre of (1 R,trans) 2,2-dimethyl 3-[2-methoxy carbonyl (E) ethenyl cyclopropane carboxylic acid chloride in benzene. 1.77 9 of the product sought are obtained.

oil = + 47.5 + 1.5 (c = 1% CHCl3).

Example 12: Methyl (1 R, cis) 2,2-dimethyl 3-[2-methoxy carbonyl (E) ethenyl] cyclopropane carboxylate.

The reaction is carried out as in Example 7, starting with 1.26 g of (1 R,cis) 2,2-dimethyl 3-(2- methoxy carbonyl (E) ethenyl] cyclopropane carboxylic acid and 12.7 cm3 of a chloromethylenic solution containing 0.5 mole/litre of diazomethane. 0.678 g of product sought is obtained.

[&alpha;]D = - 4 2 (c = 0.6% in chloroform).

Example 13: Ethyl (1R,cis) 2,2-dimethyl 3-[2-methoxy carbonyl (E) ethenylj cyclopropane carboxylate.

The reaction is carried out as in Example 3, starting with 1.51 g of (1 R,cis) 2,2-dimethyl 3-[2 methoxy carbonyl (E) ethenyl cyclpropane carboxylic acid chloride in 10 cm3 of benzene andwith 0.465 cm3 of ethanol. 0.837 g of product sought is obtained.

(aL= = - 21" f 1.5 (e = 1% CHCI,) Example 14: Isopropyl (lR,cis) 2,2-dimethyl 3-[2-methoxy carbonyl (E) ethenyl] cyclopropane carboxylate.

The reaction is carried out as in Example 3, starting with 1.51 g of (1 R,cis) 2,2-dimethyl 3-[2methoxy carbonyl (E) ethenyl] cyclopropane carboxylic acid chloride and 0.61 cm3 of isopropanol. 0.820 g of the product sought is obtained.

[&alpha;]D = - 28 1.5 (c = 1% CHCl3).

Example 15: Tertbutyl (1R,cis) 2,2-dimethyl 3-[2-methoxy carbonyl (E) ethenyl] cyclopropane carboxylate.

The reaction is carried out as in Example 3, starting with 1.51 g of (1R,cis) 2,2-dimethyl 3-(2- methoxy carbonyl (E) ethenyl] cyclopropane carboxylic acid chloride and 0.754 cm3 of tertbutanol. 0.235 g of product sought is obtained.

LaL = - 23 1.5 (c = 0.9% CHCl3).

Example 16: Benzyl (1R,cis) 2,2-dimethyl 3-[2-methoxy carbonyl (E) ethenyl] cyclopropane carboxylate.

The reaction is carried out as in Example 3, starting with 0.83 cm3 of benzyl alcohol and 1.51 g of (1 R,cis) 2,2-dimethyl 3-(2-methoxy carbonyl (E) ethenyl] cyclopropane carboxylic acid chloride. 1.046 g of product sought are obtained.

[&alpha;]D= - 56 + 1.5 (c = 0.9% CHCl3).

Example 17: Methyl (lR,trans) 2,2-dimethyl 3-r(E) (dihydro 2-oxo-3-(2H) furanylidene) methyl] cyclopropane carboxylate.

A mixture of 4.2 g of (1 R,trans) 2,2-dimethyl 3-((E) (dihydro 2-oxo-3-(2H) fruranylidene) methyl] cyclopropane carboxylic acid, 3.5 g of methyl N-(1-methylethyl) N'-(1-methylethyl) carbamimidate and about 20 cm3 of ethyl acetate is refluxed for 2 hours. It is cooled and concentrated to dryness, and the residue is chromatographed on silica, elution being carried out with a mixture of cyclohexane and ethyl acetate (6:4). 2.5 g of the product sought are thus obtained.

[&alpha;]D = +65 +2.5 (c=0.6% EtOH).

Example 18: Methyl (IR,cis) 2,2-dimethyl 3-r(E) (dihydro 2-oxo 3(2H) furanylidene) methyl] cyclopropane carboxylate.

The reaction is carried out as in Example 17, starting with 3.9 g of (1 R,cis) 2,2-dimethyl 3 ((E) (dihydro 2-oxo 3-(2H) furanylidene) methyl] cyclopropane carboxylic acid and 3.5 g of methyl N-(1-methylethyl) N'-(1-methylethtyl) carbamimidate. 1.2 g of product sought are obtained.

[&alpha;]D = +43 +2.5 (c=0.5% EtOH).

Example 19: Ethyl (1R,trans) 2,2-dimethyl 3-(E) (dihydro 2-oxo 3(2H)-furanylidene) methyl] cyclopropane carboxylate.

The reaction is carried out as in Example 17, starting with 7.8 g of (1 R,trans) 2,2-dimethyl 3 ((E) (dihydro 2-oxo 3-(2H)-furanylidene) methyl] cyclopropane carboxylic acid and 7 g of ethyl N (1-methylethyl) N'-(1-methylethyl) carbamimidate. 5 g of product sought are obtained.

[&alpha;]D =50 2 (c=0.5% EtOH).

Example 20: Ethyl (lR,cis) 2,2-dimethyl 3-r(E) (dihydro 2-oxo 3-(2H) furanylidene) methyl] cyclopropane carboxylate.

The reaction is carried out as in Example 17, starting with 3.9 g of (1 R,cis) 2,2-dimethyl 3 ((E) (dihydro 2-oxo (2H)-furanylidene) methyl] cyclopropane carboxylic acid and 3.5 g of ethyl N (1-methylethyl) N'-(1-methylethyl) carbamimidate. 1 g of product sought is obtained.

[&alpha;]D = + 29.5 (c = 0.6% EtOH).

Example 21: Isopropyl (1 R, trans) 2,2-dimethyl 3-F(E) (dihydro 2-oxo-3-(2H) furanylidene) methyl cyclopropane carboxylate.

The reaction is carried out as in Example 17, starting with 4 9 of (1 R,trans) 2,2-dimethyl 3 [(E) (dihydro 2-oxo 3-(2H)-furanylidene) methyl] cyclopropane carboxylic acid and 5 cm3 of 1methylethyl N-(1.methylethyl) N'-(1-methylethyl) carbamimidate. 3.5 g of the product sought are obtained.

[&alpha;]= + 38.5 1.5 (c = 1% EtOH).

Example 22: Isopropyl (1R,cis) Z2-dimethyl 3-r(E) (dihydro 2-oxo 3-(2H) furanylidene) methyl) cyclopropane carboxylate.

The reaction is carried out as in Example 17, starting with 8.4 g of (1 R,cis) 2,2-dimethyl 3 ((E) (dihydro 2-oxo 3-(2H) furanylidene) methyl] cyclopropane carboxylic acid and 7.45 g of 1methylethyl N-(1-methylethyl) N'-(1-methylethyl) carbamimidate. 4.96 g of product sought are obtained.

(aL = + 41 + 2.5 (c = 0.5% benzene).

Example 23: Methyl (lR,trans) 2,2-dimethyl 3-r(E) (dihydro 2-oxo-3(2H)-thienylidene) methyl] cyclopropane carboxylate.

The reaction is carried out as in Example 17, starting with 4.5 g of (1 R,trnns) 2,2-dimethyl 3 ((E) (dihydro 2-oxo 3-(2H)-thienylidene) methyl] cyclopropane carboxylic acid and 3.5 9 of methyl N-(1-methylethyl) N'-(1-methylethyl) carbamimidate. 2.2 9 of product sought are obtained.

[a]D = + 66.5 + 1.5 (c= 1.2% EtOH).

Example 24: Methyl (lR,trans) 2,2-dimethyl 3-r(E) (dihydro 2-oxo 3(2H) thienylidene) methyl] cyclopropane carboxylate.

The reaction is carried out as in Example 17, starting with 4 g of (1 R,trans) 2,2-dimethyl 3 [(E) (dihydro 2-oxo-3-(2H) thienylidene) methyl] cyclopropane carboxylic acid and 3.5 g of ethyl N-(1-methylethyl) N'-(1-methylethyl) carbamimidate. 0.8 g of product sought is obtained.

[&alpha;]D = + 63.5 1.5 (c = 1.1% EtOH).

Example 25: Ethyl (1R,cis) 2,2-dimethyl 3-f(E) (dihydro 2-oxo-3-(2H)-thienylidene methyl] cyclopropane carboxylate.

The reaction is carried out as in Example 17, starting with 9 g of (1 R,cis) 2,2-dimethyl 3-[(E) (dihydro 2-oxo 3-(2H)-thienylidene) methyl] cyclopropane carboxylic acid and 7 g of ethyl N-(1methylethyl) N'-(1-methylethyl) carbamimidate. 4.5 g of product sought are obtained.

(aL=77' + 1.5 (c= 1% benzene).

Example 26: Terbutyl (1R,trans) 2,2-dimethyl 3-C(E) (dihydro 2-oxo-3-(2H)-thienylidene) methyl] cyclopropane carboxylate.

The reaction is carried out as in Example 17, starting with 4.5 g of (1 R,trans) 2,2-dimethyl 3 ((E) (dihydro 2-oxo-3-(2H)-thienylidene) methyl] cyclopropane carboxylic acid and 5 g of tertbutyl N-(1-methylethyl) N'-(1-methylethyl) carbamimidate. 0.9 g of the product sought is obtained.

world = + 26' j 2 (c = 0.7% EtOH).

Example 27: Isopropyl (1R,cis) 2,2-dimethyl 3-F(E) (dihydro 2-oxo 3-(2H)-thienylidene) methyl] cyclopropane carboxylate.

The reaction is carried out as in Example 17, starting with 4.5 g of (1 R,cis) 2,2-dimethyl 3 ((E) (dihydro 2-oxo-3-(2H)-thienylidene) methyl] cyclopropane carboxylic acid and 5 cm3 of 1methylethyl N-(1-methylethyl) N'-(1-methylethyl) carbamimidate. 3.8 g of the product sought are obtained.

(aL= = 57 + 1.5 (e = 1% benzene).

Example 28: Methyl (1R,cis) 2,2-dimethyl 3-f(E) (dihydro 2-oxo-3-(2H)-thienylidene) methyl) cyclopropane carboxylate.

The reaction is carried out as in Example 17, starting with 4.5 g of (1 R,cis) 2,2-dimethyl 3 [(E) (dihydro 2-oxo 3-(2H)-thienylidene) methyl] cyclopropane carboxylic acid and 3.5 g of methyl N-(methylethyl) N'-(1-methylethyl) carbamimidate. 2.2 g of the product sought are obtained.

[&alpha;]D = + 63.5 1.5 (c = 1.1% EtOH).

Example 29: Methyl (1 A, cis) 2, 2-dimethyl 3-C(Z) 2-cyano ethenyl] cyclopropane carboxylate.

1.85 9 of (1 R,cis) 2,2-dimethyl 3-[(Z) 2-cyano ethenyl] cyclopropane carboxylic acid chloride are added, at 0 C, to a solution containing 2 cm3 of methanol, 10 cm3 of benzene and 1 cm3 of pyridine. The reaction solution is kept under agitation for 16 hours at 20 C. It is poured into water, extracted with benzene, dried and evaporated to dryness under reduced pressure. The residue is chromatographed on silica, elution being carried out with benzene. 0.511 g or product sought is thus obtained.

NMR Spectrum CDCI3 p.p.m.

1.3 H of the methyls at position 2 of the cyclopropane 3.7 H of the methyl at position a of the CO2 1.95-2.1 H of the carbon at position 1 of the cyclopropane 2.18-2.5 H of the carbon at position 3 of the cyclopropane 5.3-5.48 H of the carbon at position 2 of the ethenyl radical 6.8-6.9-7 H of the carbon at position 1 of the ethenyl Example 30: Ethyl (lR,trans) 2,2-dimethyl 3-C(E + Z) 2-cyano ethenyl] cyclopropane carboxylate.

A mixture containing 2 9 of (1 R,trans) 2,2-dimethyl 3-((E + Z) 2-cyano ethenyl] cyclopropane carboxylic acid, 50 cm3 of methylene chloride, 300 mg of 4-dimethylamino pryidine and 2.5 9 of dicyclohexylcarbodiimide is agitated for 30 minutes at 20 C. 1 cm3 of ethanol is added. The reaction mixture is agitated at 20 C for 16 hours. The insoluble matter is eliminated and the filtrate is washed with a 0.1 N solution of hydrochloric acid, then with water. The organic phase is dried and distilled to dryness under reduced pressure. The residue is chromatographed on silica, elution being carried out with a mixture of toluene and ethyl acetate (95:5). 0.842 9 of product sought is thus obtained.

(aL = + 46 2.5 (c = 0.6% CHCl3).

Example 31: Methyl (lR,trans) 2,2-dimethyl 3j(E+Z) 2-cyano ethenyl] cyclopropane carboxylate.

A mixture containing 1.6 g of a 60% suspension of sodium hydride in oil and 60 cm3 of tetrahydrofuran is agitated at 20 C and, over 30 minutes at a temperature between 10 and 25 C inclusive, 7.09 g of 0,0-diethyl cyano methyl phosphonate are added. The whole is agitated for 1 hour at 20 C and cooled to - 15"C, then 3.12 g of methyl (1R,trans) 2,2dimethyl 3-formyl cyclopropane carboxylate, in solution in 15 cm3 of tetrahydrofuran, are added. The solution is then agitated for 2 hours at - 15"C, then for 1 hour at 20 C. The reaction mixture is poured into a mixture of ice and 0.1 N hydrochloric acid. The whole is extracted with methylene choloride.The organic phase is washed with water until neutral, dried and distilled to dryness under reduced pressure. The residue is chromatographed on silica, eluant : benzene and ethyl acetate (95:5). 2.04 9 of the product sought are thus obtained.

[&alpha;]D = + 77 + 1.5 (c = 1 % (:HCI3).

Example 32: Benzyl (lR,trans) 2,2-dimethyl 3-r(z + E) 2-cyano ethenyl] cyclopropane carboxylate.

The reaction is carried out as in Example 30, starting with 2 9 of (1 R,trans) 2,2-dimethyl 3 ((Z + E) 2-cyano ethenyl cyclopropane carboxylic acid and 2 cm3 of benzyl alcohol. 2.9 9 of a product are obtained, which is chromatographed on silica, elution being carried out with a mixture of toluene and ethyl acetate (95:5). 700 mg of the Z isomer of the product sought and 646 mg of the E isomer of the product sought are thus isolated.

Z Isomer: Melting point: 64 C.

(aL = - 51.5 1.5 (c = 1% CHCl3).

E Isomer [&alpha;]D = +61 2.5 (c=0.5% CHCl3).

Example 33: Isopropyl (1R,trans) 2,2-dimethyl 3-f(E + Z) 2-cyano ethenyl] cyclopropane carboxylate.

The reaction is carried out as in Example 30, starting with 2 9 of (1 R,trans) 2,2-dimethyl 3 ((E + Z) 2-cyano ethenyl] cyclopropane carboxylic acid and 1.3 cm3 of isopropyl alcohol. 1.428 g of the product sought are obtained.

[&alpha;]D = + 48.5 1 (c = 1% CHCl3).

Example 34: Ethyl (1 A, cis) 2,2-dimethyl 3-(E + Z) 2-cyano ethenyl] cyclopropane carboxylate.

The reaction is carried out as in Example 30, starting with 1.65 9 of (1 R,cis) 2,2-dimethyl 3 ((E + Z) 2-cyano ethenyl] cylcopropane carboxylic acid and 2 cm3 of ethanol. 1.187 9 of product sought are obtained.

[&alpha;]D = + 44.5 2 (c = 0.6% CHCl3).

Example 35: Isopropyl (lR,cis) 2,2-dimethyl 3-r(E f Z) 2-cyano ethenyl] cyclopropane carboxylate.

The reaction is carried out as in Example 30, starting with 1.6 9 of (1 R,cis) 2,2-dimethyl 3 ((E + Z) 2-cyano ethenyl] cyclopropane carboxylic acid and 1 cm3 of isopropyl alcohol. 1.275 9 of product sought are obtained.

(aL = + 34.5" f 1.5 (c = 1% CHO3).

Example 36: Benzyl (1 R,cis) 2,2-dimethy 3-f(E + Z) 2-cyano ethenyl] cyclopropane carboxylate.

The reaction is carried out as in Example 30, starting with 1.6 9 of (1 R,cis) 2,2-dimethyl 3 [(E + Z) 2-cyano ethenyl] cyclopropane carboxylic acid and 1.5 cm3 of benzyl alcohol. 1.73 9 of product sought are obtained.

[a]D = + 12.5" + 3" (c = 0.25% CHO3).

Example 37: There will be given hereinafter the odours of a few compounds of formula (I): - compound of Example 1 : iris - compound of Example 36 : tutti frutti (mixture of fruits) - compound of Example 13 : heady, flowery - compound of Example 28 : odour of citrus fruits, grapefruit.

Example 38: Example of soaps: Toilet soaps were prepared, starting with the ingredients below (parts by weight): - commercial soap paste 1000 - product of Example 1 5 Example 39: Formulations of "Rose" compositions were prepared, starting with the ingredients below (parts by weight): - terpeneless geranium 180 - citronellal 300 - geranyl acetate 45 - nerol 15 - methylionone 15 - phenylethyl alcohol 170 - rhodinol Bourbon 60 - citronellyl acetate 40 - benzoin resin 30 - ketone musk 15 - aldehyde C 9 1/10 DPG 15 - alpha ionone 15 - product of Example 36 100 1000 Example 40: Formulations of "Opoponax" compositions were prepared, starting with the ingreadients below (parts by weight): : - bergamot 310 - synthetic neroli 20 - patchouli from which the iron has been removed 10 - rose essence 10 - vetiverol 60 - santalol 125 - castor resin 40 - coumarin 80 - gamma methylionone 75 - vanillin 40 - benzoin resin 25 - ketone musk 40 - ambrette musc 65 - product of Example 36 100 1000 Example 41: Formulations of "Jasmin" compositions were prepared, starting with the ingredients below (parts by weight): - benzyl acetate 260 - linalyl acetate 60 - phenylethyl alcohol 60 - hexylcinnamic aldehyde 90 - hydroxycitronellal 60 - benzyl salicylate 50 - methyl anthranilate 30 - linalol 45 - paracresyl phenylacetate 15 - ylang extra 50 - santal 30 - dimethyl benzyl carbinol 15 - styrax hyperessence 50 - hedione 85 - product of Example 13 100 1000 Example 42: Example of detergent powders.

- commercial detergent powders 1000 - product of Example 28 1

Claims (25)

1. Compounds of formula (I):

(in which: either one of the groups R, and R2 represents a radical -CHO, a radical -COalk, in which alk, represents an alkyl radical containing from 1 to 8 carbon atoms, a radical CO2alk2 in which alk2 represents an alkyl radical containing from 1 to 8 carbon atoms or a radical -CN, and the other of the groups R, and R2 represents a hydrogen atom, or R, and R2, together with the carbon atom to which they are bonded, from a radical

in which X represents an oxygen atom, a sulphur atom or an imino group, connected by the carbon atom at position (3) to the double bond of the vinyl substituent; and R represents either a straight or branched alkyl radical containing from 1 to 1 2 carbon atoms optioanally substituted by a cycloalkyl or cycloalkenyl radical containing from 3 to 6 carbon atoms or by a hyrdrocarbon chain containing from 2 to 8 carbon atoms and optionally interrupted by an oxygen atom or a > C = 0 group, ora straight or branched alkenyl or alkynyl radical containing from 3 to 8 carbon atoms, ora cycloaliphatic radical containing from 3 to 12 carbon atoms optionally including one or more double bonds, said cycloaliphatic radical being optionally substituted by one or more alkyl radicals, oran optionally substituted aralkyl radical containing from 7 to 1 2 carbon atoms) in all possible isomeric forms, including mixtures thereof, provided that when either R, or R2 represents a group CHO, COalk, CO2alk2 or

the double bond of the vinyl substituent of the cyclopropane ring has the geometry E.

2. Compounds of formula (I) as defined in claim 1, in which the cyclopropane acid moiety is of (1 R,trans) or (1 R,cis) structure.

3. Compounds of formula (I) as defined in claim 1 or claim 2, in which R represents a straight or branched alkyl radical containing from 1 to 4 carbon atoms.

4. Compounds of formula (I) as defined in claim 1 or claim 2, in which R represents a benzyl radical.

5. Compounds of formula (I) as defined in any one of claims 1 to 4, in which R1 or R2 represents the radical CHO.

6. Compounds of formula (I) as defined in any one of claims 1 to 4, in which R, or R2 represents the radical COCH3 or CO2CH3.

7. Compounds of formula (I) as defined in any one of claims 1 to 4, in which R1 or R2 represents the radical -C-N.

8. Ethyl (1 R, cis)-2, 2-dimethyl-3-[2-methoxycarbonyl-(E)-ethenyl]cyclopropane carboxylate.

9. Benzyl (1 R,cis)-2,2-dimethyl-3-[(E + Z)-2-cyanoethenyl]-cyclopropane carboxylate.

10. Methyl (1R,cis)-2,2-dimethyl-3-[(E)-(dihydro-2-oxo-3-(2H)-thienylidene methyl]cyclopropane carboxylate.

11. Compounds of formula (I) as defined in claim 1 as herein specifically described in any one of Examples 1 to 36.

1 2. Perfumed substances or articles containing as a perfuming agent at least one compound of formula (I) as claimed in claim 1.

1 3. A perfumed substance as claimed in claim 1 2 which is a perfuming composition useful in the preparation of perfumes and other products.

14. A perfumed substance or article as claimed in claim 1 2 which is perfume, an article of hygiene, a cosmetic, a deodorant, a detergent, a cleaning material or an insecticide.

1 5. A perfumed substance or article as claimed in any one of claims 1 2 to 1 4 containing, in addition to the compound of formula (I), one or more supporting, modifying, fixing, perserving or stabilising vehicles or one or more supports, solvents, dispersants or emulsifiers.

1 6. Perfumed substances or articles substantially as herein described.

1 7. Perfumed substances or articles substantially as herein described with reference to any one of Examples 38 to 42.

1 8. A process for preparing a compound of formula (I) as defined in any one of claims 1 to 11, in which an acid of formula (all):

in which R, and R2 are as defined in claim 1 or a functional derivative thereof, is reacted with an alcohol of formula ROH, in which R is as defined in claim 1, or a functional derivative thereof, whereby the desired compound of formula (I) is obtained.

1 9. A process for preparing a compound of formula (I) as defined in any one of claims 1 to 11 in which a compound of formula (III):

in which alk; and alk2each represents an alkyl radical containing from 1 to 4 carbon atoms and R1 and R2 are as defined in claim 1, is reacted with an aldehyde of formula (V):

in which R is as defined in claim 1, whereby the desired compound of formula (I) is obtained.

20. A process for preparing a compound of formula (I) as defined in any one of claims 1 to 11 in which a compound of formula (IV):

in which R, and R2 are as defined in claim 1, is reacted with an aldehyde of formula (V) as defined in claim 1 9 whereby the desired compound of formula (I) is obtained.

21. Processes for the preparation of compounds of formula (I) as defined in claim 1 substantially as herein described.

22. Processes for the preparation of compounds of formula (I) as defined in claim 1 substantially as herein described in Examples 1 to 36.

23. A compound of formula (I) as defined in claim 1 when prepared by a process as claimed in any one of claims 1 8 to 22.

24. A method of imparting a perfume of scent to a substance or article comprising incorporating into the said substance or article one or more compounds of formula (I) as defined in claim 1.

25. The use of the compounds of formula (I) as defined in claim 1 as perfuming agents.