GB2087384A - Cyclopropane carboxylic acid derivatives - Google Patents

Cyclopropane carboxylic acid derivatives Download PDF

Info

Publication number
GB2087384A
GB2087384A GB8129795A GB8129795A GB2087384A GB 2087384 A GB2087384 A GB 2087384A GB 8129795 A GB8129795 A GB 8129795A GB 8129795 A GB8129795 A GB 8129795A GB 2087384 A GB2087384 A GB 2087384A
Authority
GB
United Kingdom
Prior art keywords
methyl
cyclopropane
compounds
propenyl
dimethyl
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
GB8129795A
Other versions
GB2087384B (en
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Sanofi Aventis France
Original Assignee
Roussel Uclaf SA
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Roussel Uclaf SA filed Critical Roussel Uclaf SA
Publication of GB2087384A publication Critical patent/GB2087384A/en
Application granted granted Critical
Publication of GB2087384B publication Critical patent/GB2087384B/en
Expired legal-status Critical Current

Links

Classifications

    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N53/00—Biocides, pest repellants or attractants, or plant growth regulators containing cyclopropane carboxylic acids or derivatives thereof

Landscapes

  • Life Sciences & Earth Sciences (AREA)
  • Dentistry (AREA)
  • Pest Control & Pesticides (AREA)
  • Plant Pathology (AREA)
  • Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Agronomy & Crop Science (AREA)
  • General Health & Medical Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Zoology (AREA)
  • Environmental Sciences (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Cosmetics (AREA)
  • Fats And Perfumes (AREA)

Abstract

Compounds of general formula I; <IMAGE> in which R represents a saturated, linear or branched alkyl radical containing from 1 to 12 carbon atoms [optionally substituted by a cycloalkyl radical containing from 3 to 6 carbon atoms or a hydrocarbon chain containing from 2 to 8 carbon atoms (optionally interrupted by an oxygen atom or a ketone function)]; a linear or branched, alkenyl or alkynyl radical containing from 2 to 8 carbon atoms, a cycloalkyl radical containing from 3 to 12 carbon atoms (optionally containing one or more double bonds and/or substituted by one or more alkyl radicals); or an optionally substituted aralkyl radical containing from 7 to 12 carbon atoms; and R2 and R3 each represents an alkyl radical containing from 1 to 4 carbon atoms or a halogen atom, the said compounds of general formula I being in any one of the possible isomeric forms or mixtures thereof are of use as perfuming agents.

Description

SPECIFICATION Cyclopropane carboxylic acid derivatives The present invention is concerned with new derivatives of cyclopropane carboxylic acid, a process for their preparation and their use as perfuming agents.
According to one feature of the invention there are provided compounds of general formula I,
in which R represents a saturated, linear or branched alkyl radical containing from 1 to 1 2 carbon atoms [optionally substituted by a cycloalkyl radical containing from 3 to 6 carbon atoms or a hydrocarbon chain containing from 2 to 8 carbon atoms (optionally interrupted by an oxygen atom or a ketone function)]; a linear or branched, alkenyl or alkynyl radical containing from 2 to 8 carbon atoms, a cycloalkyl radical containing from 3 to 1 2 carbon atoms (optionally containing one or more double bonds and/or substituted by one or more alkyl radicals); or an optionally substituted aralkyl radical containing from 7 to 1 2 carbon atoms; and R2 and R3 each represents an alkyl radical containing from 1 to 4 carbon atoms or a halogen atom, the said compounds of general formula I being in any one of the possible isomeric forms or mixtures thereof.
The compounds of formula I may exist in numerous possible isomeric forms; in fact, they all have two asymmetrical carbons in positions 1 and 3 of the cyclopropane ring and can also possess one or more asymmetric centres or axes in the moiety.
When R represents saturated C, ,2 alkyl radical it is preferred to be a methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, n-pentyl, n-hexyl, 2-methyl-pentyl, 2, 3-dimethylbutyl, nheptyl, 2-methyl-hexyl, 2, 2-dimethyl-pentyl, 3, 3-dimethylpentyl, 3-ethylpentyl, n-octyl, 2, 2dimethylhexyl, 3,3-dimethylhexyl, 3-methyl-3-ethylpentyl, nonyl, 2,4-dimethylheptyl or n-decyl radical.
When R represents a C, 12 alkyl radical substituted by a C3 6 cycloalkyl radical or by a C2 8 hydrocarbon chain, it is preferred to be a C, ,2 alkyl radical substituted by a cyclopropyl, cyclopentyl or cyclohexyl radical or by a cyclopentenyl or cyclohexenyl radical.
When R represents a C28 alkenyl radical, it is preferred to be a butenyl, isobutenyl or crotonyl radical.
When R represents a C28 alkynyl radical, it is preferred to be an ethynyl or a propynyl radical.
When R represents a C3 ,2 cycloalkyl radical, it is preferred to be a cyclopropyl, cyclopentyl, cyclohexyl, cycloheptyl or cyclooctyl radical.
When R represents a C3 ,2 cycloalkyl radical containing one or more double bonds, it is preferred that it contains two double bonds.
When R represents a C3 ,2 cycloalkyl radical substituted by one or more alkyl radicals, it is preferred to be a C3 ,2 cycloalkyl radical substituted by one or more methyl, ethyl or n-propyl radicals.
When R represents an optionally substituted C7 ,2 aralkyl radical, it is preferred to be a benzyl or phenyl-ethyl radical, optionally substituted in the ortho, meta or para positions by one or more substituents selected from alkyl radicals containing from 1 to 4 carbon atoms, alkoxy radicals containing from 1 to 4 carbon atoms, such for example methoxy, halogen atoms such, for example, chlorine or fluorine and trifluoromethyl radicals.
When R2 and/or R3 represents an alkyl radical, it is preferred to be a methyl, ethyl or n-propyl radical.
When R2 and/or R3 represents a halogen atom, it is preferred to be a fluorine or chlorine atom.
A particular subject of the invention is the compounds of formula I in which R represents a linear or branched alkyl radical containing from 1 to 4 carbon atoms. Also preferred are those compounds in which R represents an alkenyl or an alkynyl radical containing from 2 to 6 carbon atoms, as well as those in which R represents a benzyl or a phenyl-ethyl radical.
In particular, the invention has as its subject the compounds of formula I, in which R2 and R3 are identical and especially those in which R2 and R3 are methyl, fluorine or chlorine.
More particularly, the subject of the invention is those compounds for which the preparation is given further on in the experimental part, and especially: 1 -methyl-ethyl (1 R,trans)-2, 2-dimethyl-3-(2-methyl- 1 -propenyl)-cyclopropane carboxylate, crotonyl (1 R,trans)-2, 2-dimethyl-3-(2-methyl- 1 -propyenyl)-cyclopropane-carboxylate, 1 -(3-butenyl) (1 R,trans)-2, 2-dimethyl-3-(2-methyl-1 -propenyl)-cyclopropane-carboxylate, 2-phenylethyl (1 B,trans)-2, 2-dimethyl-3-(2-methyl- 1 -propenyl)-cyclopropane-carboxylate, 1-methyl-ethyl ( 1 S,trans)-2, 2-d imethyi-3-(2-methyl- 1 -propenyl)-cyclopropane-carboxylate, (RS) 3-( 1 -butylene) (1 S,trans)-2, 2-dimethyl-3-(2-methyl-1 -propenyl)-cyclopropane-carboxylate, isopropyl (1 S,cis)-2, 2-dimethyl-3-(2-methyl- 1 -propenyl)-cyclopropane-carboxylate, 1 -(3-butenyl) (1 S,cis)-2, 2-dimethyl-3-(2-methyl-1 -propenyl)-cyclopropane-carboxylate, methyl ( R,cis)-2, 2-d imethyl-3-(2, 2-d ifl uoro- 1 -ethenyl)-cyclopropane-carboxylate, methyl (1 R,cis)-2, 2-dimethyl-3-(2, 2-dichlorovinyl)-cyclopropane-carboxylate.
According to a further feature of the invention there is provided a process for the preparation of the compounds of formula I, which comprises reacting an acid of formula 11,
(in which R2 and R3 are as hereinbefore defined), or a functional derivative of this acid, with an alcohol of formula lil, ROH (Ill) (in which R is as hereinbefore defined), or a functional derivative of this alcohol, whereby the desired compound of formula I is obtained.
Functional derivatives of the acid which may be used include preferably the acid chloride and the anhydride.
More particularly, the subject of the invention is a process wherein the acid chloride of the acid of formula 11 is reacted with the alcohol of formula lil. Other standard methods of preparing esters of cyclopropane carboxylic acids can also, of course, be used.
The compounds of formula I exhibit useful organoleptic properties which enable them to be used particularly as perfuming agents.
The compounds of formula I have agreeable odours, for example, a floral or flower odour or a green, woody or spicy odour. The experimental part which appears further on indicates in a more exact manner the odours given off by certain products with the formula I, (see Example 56).
Thus, the invention also has as its subject, the products with the formula I as perfuming agents, and particularly among these, the preferred products previously mentioned.
Because of their useful olfactory properties, the products with the formula I can be utilized as odoriferous agents in perfumery, to prepare odoriferous compositions which can themselves serve as bases for perfumes.
According to a further feature of the invention there is provided a method of perfuming an article or composition which comprises incorporating in the said article or composition an effective amount of a compound of formula I.
According to a yet further subject of the invention there are provided perfumed compositions containing, as a perfuming agent, at least one compound of formula I. Such compositions may be formulated, for example, in a form suitable for hygienic, cosmetic, disinfectant, maintenance or insecticidal use.
Such compositions may thus, for example, be in the form of articles of hygiene such as soaps, talcs, shampoos, deritifrices, bath salts, foam baths, bath oils and deodorants; in the form of cosmetic products such as creams, perfumes, cleansing milks, lotions, make-up materials, iipsticks and nail-varnishes; in the form of detergent materials, such as washing solutions; in the form of maintenance products such as waxes; or in the form of insecticides.
The compounds of formula I can supply a scent to odourless products; they can also bring up, increase or modify the odour of compositions which themselves have a certain odour.
Furthermore, as with any product offering an agreeable odour, they can be used to mask a disagreeable odour of a product. Naturally, such perfumed compositions may be manufactured according to the usual techniques in the industries concerned. These techniques are widely described in the specicalist literature, and in this connection there are no particular developments.
As will be further appreciated these compositions may in addition to the compounds of formula I, contain conventional additices such as e.g. vehicles, modifiers, fixatives, preservatives, stabilisers and other ingredients such as supports, solvents, dispersants and emulsifiers currently used in the industries concerned.
As regards products utilized in perfumery, there can be added to the compounds of formula I other products well known to perfumers, including natural products, such as essential oils of vetiver, cedar, bergamot, pine-needles, citrus, jasmine or mandarine and synthetic products, such as aldehydes currently utilized in perfumery such as hydroxycitronella, ketonnes such as 1'&alpha;- ionone, phenol compounds such as eugenol, alcohols such as geraniol, and lactones such as coumarin.The amount of compound of formula I to be used varies strongly as a function of the nature of the product chosen, its intended usage, and the intensity of odour which is desired, as well, naturally, as is the nature and the composition of the other ingredients which are added to the compound with the formula For example, in the case of detergents, from 0.1 % to 2% by weight of the compound of formula I can be used. In the case of perfumes, for example, there can be used from 0.1% to 10% by weight of the compounds of formula I. When the compounds of formula I are used as the base for perfumes, up to 20% by weight of these products can be used.
The following examples illustrate the invention without nevertheless, limiting it.
Example 1: 1-methyl-ethyl (1 R trans)-2, 2-dimethyl-3-(2-methyl- 1 -propenyl)-cyclopropane-car- boxylate.
A mixture of 100 ml of isopropanol and 13 ml of pyridine is cooled to 0 to + 5 C. 15 g of (1R trans)-2,2-dimethyl-3-(2-methyl-1-propenyl)-cyclopropane-carboxylic acid chloride is then added. The reaction mixture is maintained under agitation for one hour, then water is added and it is extracted with methylene chloride. The organic phases are washed with hydrochloric acid, with water, and with a 5% aqueous solution of sodium bicarbonate. After drying and concentrating, 12.42 g of the desired product is obtained after distillation. M.Pt. 90 C. (4.5 mm of Hg) [aY0: 30 + 1,5 (c = 1% toluene).
Example 2: 3-buten- 1-yl (1 R trans)-2,2-dimethyl-3-(2-methyl-1-propenyl)-cyclopropane-carboxy late.
At 0 C, 1.5 g of 1-buten-4-ol in 3.7 g of (1 B trans)-2-dimethyl-3-(2-methyl-1-propenyl)cyclopropane-carboxylic acid chloride is introduced into hexamethyl phosphotriamide; this is maintained under agitation for 1 hour at 0 C and then for 18 hours at ambient temperature, and it is then poured into water. After extracting with hexane, drying the organic phases, filtering and concentrating, then chromatographing on silica (eluant: essence G-ether, 9-1) and re-uniting the fractions with Rf = 0.45 and concentrating, 2.1 g of the product sought is obtained.
[a]D: 23 5 + 1 5 (c = 1% benzene).
Example 3 : 2-phenylethyl (1R transJ-2,2-dimethyl-3-(2-methyl-1-propenyl-cyclopropane carboxyfate.
12 g of (1R trans)-2-dimethyl-3-(2-methyl-1-propenyl)-cyclopropane-carboxylic acid chloride is introduced into a solution containing 8.5 ml of phenylethyl alcohol and 50 ml of dichlorethane.
The reaction medium is heated at reflux for 490 minutes and the solvents are evaporated.
19.16 g of a product is obtained which is distilled under reduced pressure. In this way 7.42 g of the product sought is obtained. B.Pt : 148"C (1.5 mm of Hg).
[]D20: - 1205 + 1 (c = 1.4% toluene).
Example 4: Crotonyl (1R trans)-2,2-dimethyl-3-(2-methyl-1-propenyl)-cyclopropane-carboxylate.
At 0 C, 1.6 g of crotol alcohol in 3.75 g of (1R trans)-2,2-methyl-3-(2-methyl-1-propenyl)cyclopropane-carboxylic acid chloride is introduced into 25 cm of HMPT, and the whole is kept under agitation for 48 hours at ambient temperature, after which it is poured into water and extracted with hexane. After drying, separating the solids and concentrating, an oil is obtained which is chromatographed on silica (eluant: petroleum ether (B.Pt, 40-70"C) and diethyl ether 9-1). The fractions with Rf = 0.6 are re-united and concentrated. 2.8 9 of the product sought is obtained.
[aL : -27 + 1 (c = 1.5% benzene).
Example 5: Ethyl (1R cis)-2,2-dimethyl-3-(2-methyl-1-propenyl)-cyclopropane-carboxylate 4.95 g of ethanol and 17 g of pyridine are introduced into 25 ml of benzene. Then at + 15 to + 20 C, 20 g of (1R cis)-2,2-dimethyl-3-(2-methyl-1-propenyl)-cyclopropane-carboxylic acid chloride in 20 ml of benzene is introduced. After agitation for one night at ambient temperature, 50 ml of water is added, and by decanting, washing with water, drying and distilling to dryness, a brown oil is obtained which is chromatographed on silica (eluant : heptane). 1 2.8 g of the product sought is obtained.
[&alpha;]D: + 47 5 + 1 5 (c = 1.2% ethanol).
Example 6: 1-methyl-ethyl (1R cis)-2,2-dimethyl-3-(2-methyl-1-propenyl)-cyclopropane-carboxylate.
At + 10 to + 15 C, 20 g of (1R cis)-2,2-dimethyl-3-(2-methyl-1-propenyl)-cyclopropane- carboxylic acid chloride in 20 cm3 of benzene is added to a solution containing 6 g of isopropanol, 17 9 of pyridine and 40 cm3 of benzene. After maintaining under agitation for 72 hours, 50 cm3 of heptane and 50 cm3 of water are added, and the mixture is agitated. Then by decanting, washing with hydrochloric acid, water and sodium bicarbonate, drying the organic phases, passing on silica with elution by heptane and distilling the solution to dryness, 9.3 9 of the product sought is obtained.
Fa]2n0: + 42 + 1 5 (c = 1% ethanoi).
Example 7: :1-methyl-ethyl (IS trans)-2,2-dimethyl-3-(2-methyl-1-propenyl)-cyclopropane-car- boxylate.
At 0 C, 1 cm3 of pyridine is introduced into a solution containing 3.7 9 of (1 S trans)-2,2 dimethyl-3-(2-methyl-1-propenyl)-cyclopropane-carboxylic acid, 20 cm3 of benzene and 1.5 9 of isopropanol. After agitation for 24 hours, at ambient temperature, the reaction mixture is poured into 20 cm3 of 2N hydrochloric acid. then decanted and washed with a 2N solution of sodium hydroxide. By drying, concentrating to dryness, chromatographing on silica (eluant : benzene) and re-uniting the fractions with Rf = 0.33 and concentrating, 2.4 g of the product sought is obtained.
NMR Spectrum (CDC1J) -peaks at 1.13 and 1.27 p.p.m. - H of the paired methyls of the cyclopropane -peak at 1.3 - 1.4 p.p.m. - H in position 1 of the cyclopropane.
-peak at 1.92 - 2.08 p.p.m., - H in position 3 of the cyclopropane -peak at 4.83 - 4.97 p.p.m., - H in position 1 of the propenyl Multiplet at 5.03 p.p.m., - H carried by the carbon in a of the carboxyl -peaks at 1.18 - 1.3 p.p.m. - H carried by the carbons in ss of the carboxyl.
Example 8 : (RS) 3-buten-2-yl (1S trans)-2,2-dimethyl-3-(methyl- 1-propenyl)-cyclopropane-carboxylate.
3.75 g of (1S trans)-2,2-dimethyl-3-(2-methyl-1-propenyl)-cylcopropane-carboxylic acid chloride and 1.45 9 of 1-bueen-3-ol are introduced into 50 cm3 of anhydrous benzene. After cooling to 0 C, 2 cm3 of pyridine is added drop by drop, and after agitation for 18 hours at ambient temperature, the mixture is poured into a 2N solution of hydrochloric acid. By drying on sodium sulphate and concentrating to dryness, 4.6 9 of a product is obtained which is chromatographed on silica (eluant: essence G-diethyl ether 9-1). The fractions with Rf = 0.32 are re-united and concentrated, and 2.3 g of the product sought is obtained.
[n]D24: 1.4662 Example 9: 3-buten-1-yl (1S cis)-2,2-dimethyl-3-(2-methyl-1-propenyl)-cyclopropane-carboxylate.
At 0 C, 2 g of 3-buten-1-ol are introduced into a mixture of 3.79 g of (1S cis)-2,2-dimethyl-3 (2-methyl-1-propenyl)-cyclopropane-carboxylic acid chloride and 7.8 9 of HMPT. This is agitated for 1 hour at 0 C and 1 8 hours at ambient temperature, then poured into water and extracted with hexane. The organic phases are dried, filtered and concentrated, then chromatographed on silica (eluant: petroleum ether (B.Pt. 40 - 70 C) and diethyl ether, 9-1). The fractions with Rf = 0.5 are re-united and concentrated, and 2.7 9 of the product sought is obtained.
[a]D = -40 + 2 (c = 0.7% benzene).
Example 10 : Methyl (1 R cisl-2, 2-dim eth yl-3-(2, 2-difluorovin yl)-cyclopropane-carboxylate.
About 50 cm3 of a solution of diazomethane in methylene chloride is introduced into a solution containing 3.2 g of (1 R cis)-2,2-dimethyl-3-(2,2-difiuorovinyl)-cyclopropane carboxylic acid and 20 cmJ of methylene chloride, and the solution obtained is concentrated. The oil obtained is chromatographed on silica (eluant: petroleum ether (B.Pt. 40 - 70 ) and diethyl ether 9-1). the fractions with Rf = 0.5 are re-united and concentrated, and in this way 3.4 g of the product sought is obtained.
[&alpha;]D: + 6 5 j 1 (c = 1.7% benzene).
Examples 11 to 41 By operating in the same way as in the preceding examples, the following compounds I have been prepared, starting with the compounds ll and the compounds III.
Compounds II Compounds III Compounds I Example 11: (1R cis)-2,2-dimethyl- Ethyl alcohol Ethyl (1R cis)-2,2-dimethyl-3-(2,2-difluorovinyl)3-(2,2-difluorovinyl)-cyclo- cyclopropane-carboxylate propane-carboxylic acid NMR Spectrum, (CDCl3) chloride - Peaks at 1.22 p.p.m. - H of the methyl in position 2 of the cyclopropane.
- Peak at 1.6 to 1.97 p.p.m. - H in positions 1 and 3 of the cyclopropane - Peak at 4.35 - 4.48 p.p.m.) ) - H of the ethenyl at 4.77 - 4.9 p.p.m.) - Peak at 1.15 - 1.38 p.p.m.) - H of the ethyl at 3.93 - 4.28 p.p.m.) Example 12: (1R cis)-2,2-dimethyl- 3-buten-1-ol 3-buten-1-yl (1R cis)-2,2-dimethyl- 3-(2-methyl3-(2-methyl-1-propenyl)-cyclo- -1-propenyl)-cyclopropane-carboxylate propane-carboxylic acid NMR Spectrum (CDCl3) chloride - Peaks at 1.2 to 1.23 p.p.m. - H of the paired methyls of the cyclopropane.
- Peak at 1.55 - 2 p.p.m. - H in position 1 and 3 of the cyclopropane.
- Peak at 5.08 - 5.42 p.p.m. - H in position 1 of the propenyl.
- Peak at 3.97 to 4.42 p.p.m. - H carried by the C in &alpha; of the carboxyl.
Compounds II Compounds III Compounds I -Peak at 1.7 to 1.75 p.p.m. - H in position 3 and H of the methyl in 2 of the methyl propenyl -Peak at 2.17 to 2.53 p.p.m. - H carried by the C in ss of the carboxyl -Peak at 4.83 to 6.17 p.p.m. - H carried by the ethylenci carbone of buten Example 13: (1R cis)-2,2-dimethyl- 2-cyclohexenol (1R cis)-2,2-dimethyl-3-(2-methyl-1-propenyl)3-(2-methyl-1-propenyl)- cyclopropane-carboxylate of (RS)2-cyclohexenyl cyclopropane-carboxylate NMR Spectrum (CDCl3) acid chloride -Peaks at 1.18 and 1.23 p.p.m. - H of the geminal CH3's of the cyclopropane -Peak at 0.92 ~ 2.17 p.p.m. - H in positions 1 and 3 of the cyclopropane -Peaks at 1.68 and 1.73 p.p.m. - H in positions 3 and H of the CH3 in position 2 of the propenyl -Peak at 5.08 ~ 6.08 p.p.m. - H in positions 1 of the propenyl -Peak from 5.08 to 6.08 p.p.m. - H carried by the carbon of the cyclohexenyl situated in the &alpha; position of the carboxyl -Peak from 5.08 to 6.08 p.p.m. - ethylenci H's of the cyclohexenyl -Peaks at 0.92 to 2.17 p.p.m. - other H's of the cyclohexenyl
Compounds II Compounds III Compounds I Example 14: (1R,cis)-2,2-dimethyl- Phenylethanol (1R,cis)-2,2-dimethyl-3-(2-methyl-1-propenyl)3-(2-dimethyl-1-propenyl)- cyclopropane-carboxylate of 2-phenyl-ethyl cyclopropane-carboxylic NMR Spectrum (CDCl3) acid chloride -Peak at 1.53 to 2.02 p.p.m. - H in positions 1 and 3 of the cyclopropane -Peak at 5.32 to 5.43 p.p.m. - H in position 1 of the propenyl -Peak at 4.17 to 4.4 p.p.m. - H carried by the C in position &alpha; of the carboxyl -Peak at 2.78 to 3.02 p.p.m. - H carried by the C in position ss of the carboxyl -Peak at 7.25 p.p.m. - H of the phenyl nucleus -Peaks at 1.15 and 1.18 p.p.m. - H of the geminal methyls of the cyclopropane -Peaks at 1.67 and 1.72 p.p.m. - H in position 3 and H of the methyl in position 2 of the propenyl Example 15: (1R,cis)-2,2-dimethyl- 1-ol-3-butyne (1R,cis)-2,2-dimethyl-3-(2-methyl-1-propenyl)3-(2-methyl-1-propenyl)- cyclopropane-carboxylate of 3-butyn-1-yl cyclopropane-carboxylic NMR Spectrum (CDCl3) acid chloride -Peak at 1.58 p.p.m., 2.03 p.p.m. - H in position 1 of the cyclopropane -Peak at 5.3 to 5.42 p.p.m. - H in position 1 of the propenyl
Compounds II Compounds III Compounds I -Peak at 4.03 to 4.27 p.p.m. - H carried by the C in position &alpha; of the carboxyl -Peak at 2.37 to 2.63 p.p.m. - H carried by the C in position ss of the carboxyl -Peak at 1.95 to 2.02 p.p.m. - H carried by the terminal C of the propenyl Peaks at 1.2 and 1.23 p.p.m. - H of the geminal methyls of the cyclopropane -Peaks at 1.95, 1.98 and 2.01 p.p.m. - H in position 4 of butynyl Example 16: (1R,cis)-2,2-dimethyl- 1-hydroxy 4- (1R,cis)-2,2-dimethyl-3-(2-methyl-1-propenyl)3-(2-methyl-1-propenyl)- -pentan-4-one cyclopropane-carboxylate of (4-oxo-1-pentyl) cyclopropane-carboxylic NMR Spectrum (CDCl3) acid chloride -Peak at 1.55 to 2.13 p.p.m. - H in positions 1 and 3 of the cyclorpopane and carried by the C in position ss of the carboxyl -Peak at 5.32 to 5.45 p.p.m. - H in position 1 of the propenyl -Peak from 3.95 to 4.15 p.p.m. - H carried by the C in position &alpha; of the carboxyl -Peaks from 2.42 to 2.62 p.p.m. - H carried by the C position &gamma; of the carboxyl -Peak at 2.13 p.p.m. - H carried by the terminal methyl of the pentyl -Peaks from 1.18 to 1.22 p.p.m. - H of the geminal methyls of the cyclopropane
Compounds II Compounds III Compounds I -Peaks at 1.67 and 1.73 p.p.m. - H in position 3 and H of the methyl in position 2 of the propenyl Example 17: (1S,trans)-2,2-dimethyl- Cyclohexylmethyl (1S,trans)-2,2-dimethyl-3-(2-methyl-1-propenyl)3-(2-methyl-1-propenyl)- alcohol cyclopropane-carboxylate of cyclohexyl-methyl cyclopropane-carboxylic /n/D19.5: 1.4832 acid chloride Example 18: (1S,trans)-2,2-dimethyl- 3-hexen-1-ol (1S,trans)-2,2-dimethyl-3-(2-methyl-1-propenyl)3-(2-methyl-1-propenyl)- cyclopropane-carboxylate of cis 3-hexen-1-yl cyclopropane-carboxylic /n/D20: 1.4746 acid chloride
Compounds II Compounds III Compounds I Example 19: (1R cis)-2,2-dimethyl- Cyclohexanol Cyclohexyl (1R cis)-2,2-dimethyl-3-(2-methyl3-(2-methyl-1-propenyl)- 1-propenyl)-cyclopropane-carboxylate cyclopropane-carboxylic NMR (CDCl3) acid chloride -Peaks at 1.2 and 1.24 p.p.m. - H of the paired cyclopropane.
-Peaks at 4.72 p.p.m. - H carried by the cyclohexyl carbon in &alpha; of CO2 -Peak at 5.32 to 5.45 p.p.m. - H in position 1 of propenyl -Peaks at 1.72 p.pm. - H in position 3' and H of methyl in position 2 of propenyl
Compounds II Compounds III Compounds I Example 20: (1S trans)-2,2-dimethyl- 3-butyne-1-ol (1S trans)-2,2-dimethyl-3-(2-methyl3-(2-methyl-1-propenyl)- 1-propenyl)-cyclopropane-carboxylate of cyclopropane-carboxylic 3-butyn-1-yl acid chloride /n/D19: 1.4791 Example 21 (1S cis)-2,2-dimethyl- Isopropanol (1S cis)-2,2-dimethyl-3-(2-methyl-1-propenyl)3-(2-methyl-1-propenyl)- cyclopropane-carboxylate of 1-methyl-ethyl cyclopropane-carboxylic NMR spectrum (CDCl3) acid chloride -Peak at 1.5 to 2 p.p.m. - H in position 1 and 3 of the cyclopropane -Peaks at 1.2 and 1.3 p.p.m. - H of the paired methyls of the cyclopropane
Compounds II Compounds III Compounds I -Peak at 5.3 to 5.45 p.p.m. - H in position 1 of the propenyl -Multiplet at 4.64 p.p.m. - H carried by the in position &alpha; of the carboxyl -peak at 1.17 to 1.27 p.p.m. - H of the methyl of l' isopropyl Example 22: (1S cis)-2,2-dimethyl- Methanol Methyl (1S cis)-2,2-dimethyl-3-(2-methyl3-(2-methyl-1-propenyl)- 1-propenyl)-cyclopropane-carboxylate cyclopropane-carboxylic acid /&alpha;/D: -67.5 # 1.5 (c = 1 % methanol) chloride Example 23: (1S trans)-2,2-dimethyl- Benzylic alcohol Benzyl (1S trans)-2,2-dimethyl-3-(2-methyl3 (2-methyl-1-propenyl) 1-propenyl)-cyclopropane-carboxylate cyclopropane-carboxylic /&alpha;/D: 8 # 2 (C = 1.2 % CH3OH) acid chloride /n/D22: 1,5162 Example 24: (1S cis)-2,2-dimethyl- Cyclopropyl- Cyclopropyl-methyl (1S cis)-2,2-dimethyl3-(2-methyl-1-propenyl- methanol 3-(2-methyl-1-propenyl)-cyclopropanecyclopropane-carboxylic carboxylate acid chloride /&alpha;/D: -34 # 1 (c = 0.96 ClH)
Compounds II Compounds III Compounds I Example 25: (1S trans)-2,2-dimethyl- Cyclopropyl- Cyclopropyl-methyl (1S trans)-2,2-dimethyl3-(2-methyl-1-propenyl)- methanol 3-(2-methyl-1-propenyl)-cyclopropanecyclopropane-carboxylic carboxylate acid chloride /nD19.5: 1.4769
Compounds II Compounds III Compounds I Example 26: (1R trans)-2,2-dimethyl- Cyclopropylmethanol Cyclopropyl-methyl (1R trans)-2,2-dimethyl3-(2-methyl-1-propenyl)- 3-(2-methyl-1-propenyl)-cyclopropanecyclopropane-carboxylic carboxylate acid chloride /&alpha;/D: -29.5 # 2 (c = 0.8 % benzene) Example 27 (1S trans)-2,2-dimethyl- Methanol Methyl (1S trans)-2,2-dimethyl-3-(2-methyl3-(2-methyl-1-propenyl)- 1-propenyl)-cyclopropane-carboxylate cyclopropane-carboxylic acid /&alpha;/D: -17 # 1 (c = 1 % CH3OH) Eb.: chloride 34 C/2 mm Hg
Compounds II Compounds III Compounds I Example 28: (1R cis)-2,2-dimethyl- Benzylic Alcohol Benzyl (1R cis)-2,2-dimethyl-3-(2-methyl3-(2-methyl-1-propenyl)- 1-propenyl)-cyclopropane-carboxylate cyclopropane-carboxylic /&alpha;/D: +17 # 1 (c = 1 % ethanol) acid chloride Example 29: (1R trans)-2,2-dimethyl- 3-butyn-1-ol 3-butyn-1-yl (1R trans)-2,2-dimethyl3-(2-methyl-1-propenyl)- 3-(2-methyl-1-propenyl)-cyclopropanecyclopropane-carboxylic carboxylate acid chloride /&alpha;/D: -20 # 1 (c = 1.5 % benzene)
Compounds II Compounds III Compounds I Example 30: (1R cis)-2,2-dimethyl-3(2- Methanol Methyl (1R cis)-2,2-dimethyl-3-(2-methylmethyl-1-propenyl)-cyclo- 1-propenyl)-cyclopropane-carboxylate.
propane-carboxylic acid [&alpha;]D = + 65 # 1 , (c = 2 % CH3OH) chloride B.Pt: 37 C / 0.2 mm Hg.
Example 31 (1R trans)-2,2-dimethyl3-(2-methyl-1-propenyl)cyclopropane-carboxylic acid chloride Benzyl alcohol Benzyl (1R trans)-2,2-dimethyl-3-(2-methyl1-propenyl)-cyclopropane-carboxylate.
[&alpha;]D = -9 # 1 , (c = 1.2 % methanol) Example 32 (1R trans)-2,2-dimethyl- 1-(3-cis)-hexanol (3-cis)-hexenyl (1R trans)-2,2-dimethyl -methyl-1-propenyl)-cyclo- 3-(2-methyl-1-propenyl)-cyclopropanepropane-carboxylic acid carboxylate.
chloride. [&alpha;]D = -17 # 1 , (c = 1 % C6H6)
Compounds II Compounds III Compounds I Example 33 (1R trans)-2,2-dimethyl- Methoxyethanol 2-methoxy-ethyl (1R trans)-2,2-dimethyl3-(2-methyl-1-propenyl)- 3-(2-methyl-1-propenyl)-cyclopropanecyclopropane-carboxylic carboxylate.
acid chloride NMR Spectrum, (CDCl3) - peaks at 1.2 and 1.27 p.p.m., - H of the paired methyls of the cyclopropane - peak at 1.7 p.p.m., H in position 3 and H of the methyl in position 2 of the propenyl.
- peak at 1.4 - 1.5 p.p.m. - H in position 1 of the cyclopropane - peak at 1.02 - 2.15 p.p.m. - H in position 3 of the cyclopropane.
- peak at 4.83 - 4.97 p.p.m. - H in position 1 of the propenyl, - peak at 4.13 - 4.28 p.p.m. - H carried by the C in position &alpha; of the carboxyl - peak at 3.5 - 3.63 p.p.m. - H carried by the C in position ss of the carboxyl - peak at 3.38 p.p.m., - H of the methoxy.
Example 34 (1S cis)-2,2-dimethyl-3-(2- 3-cis-hexen-1-ol 3-(cis)-hexenyl (1S cis)-2,2-dimethyl-3-(2 -methyl-1-propenyl)-cyclo- methyl-1-propenyl)-cyclopropane-carboxylate.
Compounds II Compounds III Compounds I Example 34 (contd) propane-carboxylic acid [&alpha;]D = -35 # 1 (c = 2 % benzene).
chloride Example 35 : (1R trans)-2,2-dimethyl- (RS)cyclohexanol (RS)2-cyclohexenyl (1R trans)-2,2-dimethyl3-(2-methyl-1-propenyl)- 3-(2-methyl-1-propenyl)-cyclopropane-carboxylcyclopropane-carboxylic ate.
acid chloride. [&alpha;]D = -40 5 # 1 5 (c = 1.2 % benzene) Example 36 (1S cis)-2,2-dimethyl-3-(2- Methoxyethanol (2-methoxy)-ethyl (1S cis)-2,2-dimethyl -methyl-1-propenyl)-cyclo- 3-(2-methyl-1-propenyl)-cyclopropanepropane-carboxylic acid carboxylate.
chloride. [&alpha;]D = -25 5 # 1 (c = 1 % benzene).
Compounds II Compounds III Compounds I Example 37 (1S trans)-2,2-dimethyl- Crotol alcohol Crotonyl (1S trans)-2,2-dimethyl-3-(2-metghyl3-(2-methyl-1-propenyl- 1-propenyl)-cyclopropane-carboxylate.
cyclopropane-carboxylic [&alpha;]D = + 27 + 1 (c = 1.2 % benzene).
acid chloride.
Example 38 : fi-phenyl-ethyl ( 1 R trans)-2, 2-dimethyl-3-(2-methyl- 1 -propenyl)-cyclopropane-carboxylate (example 3 product).
3.7 g of (1R trans)-2,2-dimethyl-3-(2-methyl-1-propenyl)-cyclopropane-carboxylic acid chloride, 7.6 9 of HMPT and 2.5 g of 2-phenol-ethanol are agitated for 1 hour at 0 C. The reaction mixture is then agitated for 18 hours at ambient temperature, after which it is poured into water and extracted with ether. The organic phases are dried and concentrated to dryness, then chromatographed on silica (eluant : essence G, ether, 9-1). In this way 3.3 9 of the product sought is obtained.
[&alpha;]D = -17 5 # 1 5 (c = 0.85% benzene).
Example 39 Compound II Compound III Compound (1 R trans)-2,2-di- 3-buten-2-ol 3-buten-2-yl (1 R trans)methyl-3-(2-methyl- 2, 2-dimethyl-3-(2-methyl- 1-propenyl)-cyclo- 1-propenyl)-cyclopropane propane-carboxylic carboxylate.
acid [&alpha;]D = 24 # 0 5 (c = 3% benzene).
Compounds II Compounds III Compounds I Example 40: (1R trans)-2,2-dimethyl- R-menthol R-menbthyl (1R trans)-2,2-dimethyl-3-(2-methyl3-(2-methyl-1-propenyl)-cyclo- 1-propenyl)-cyclopropane-carboxylate. propane-carboxylic acid. [&alpha;]D = -77 # 1 (c = 1.5 % benzene). Example 41: (1S trans)-2,2-dimethyl- R-menthol R-menthyl (1R trans)-2,2-dimethyl-3-(2-methyl3-(2-methyl-1-propenyl)- 1-propenyl)-cyclopropane-carboxylate. cyclopropane carboxylic [&alpha;]D = -34 5 # 2 (c = 0.6 % benzene). acid. Example 42: (1R cis)-2,2-dimethyl- R-menthol R-menthyl (1R cis)-2,2-dimethyl-3-(2-methyl3-(2-methyl-1-propenyl)- 1-propenyl)-cyclopropane-carboxylate. cyclopropane carboxylic M.Pt. = 44 C. acid
Compounds II Compounds III Compounds I Example 43: (1R trans)-2,2-dimethyl- S-menthol S-menthyl (1R trans)-2,2-dimethyl-3-(2-methyl3-(2-methyl-1-propenyl)- 1-propenyl)-cyclopropane-carboxylate. cyclopropane-carboxylic [&alpha;]D = -4 5 # 1 (c = 2 % benzene). acid Example 44: (1R trans)-2,2-dimethyl- Allyl alcohol Allyl (1R trans)-2,2-dimethyl-3-(2-methyl3-(2-methyl-1-propenyl)- 1-propenyl)-cyclopropane-carboxylate. cyclopropane-carboxylic [&alpha;]D = -19 (c = 1 % toluene) acid Example 45:: (1S cis)-2,2-dimethyl- Phenyl-ethyl 2-phenyl-ethyl (1S cis)-2,2-dimethyl-3-(2-methyl3-(2-methyl-1-propenyl)- alcohol. 1-propenyl-cyclopropane-carboxylate. cyclopropane-carboxylic [&alpha;]D = -25 # 1 (c = 2 % benzene). acid.
Compounds II Compounds III Compounds I Example 46: (1S trans)-2,2-dimethyl- 3-buten-1-ol 3-buten-1-yl (1S trans)-2,2-dimethyl3-(2-methyl-1-propenyl)- 3-(2-methyl-1-propenyl)-cyclopropanecyclopropane-carboxylic carboxylate. acid. [&alpha;]D: + 23 5 # 2 5 (c = 0.5 % benzene).
Compounds II Compounds III Compounds I Example 47: (1R cis)-2,2-dimethyl- 3-buten-2-ol 3-buten-2-yl (1R cis)-2,2-dimethyl-3-(2-methyl3-(2-methyl-1-propenyl- 1-propenyl)-cyclopropane-carboxylate. cyclopropane-carboxylic [&alpha;]D = + 33 5 # 1 5 (c = 1.2 % benzene. acid. Example 48: (1S cis)-2,2-dimethyl- Benzyl alcohol benzyl (1S cis)-2,2-dimethyl-3-(2-methyl3-(2-methyl-1-propenyl- 1-propenyl)-cyclopropane-carboxylate. cyclopropane-carboxylic NMR Spectrum (CDCl3) acid. - peaks at 1.2 and 1.23 p.p.m., - H of the methyls in position 2 of the cyclopropane. - peak at 5.1 p.p.m., - H of the methyl in position &alpha; of CO2. Example 49: (1R trans)-3-(2,2-difluoro- Ethanol Ethyl (1R trans)-3-(2,2-difluorovinyl)vinyl)-cyclopropane-carboxylic cyclopropane-carboxylate. acid. NMR Spectrum - peaks at 1.15 and 1.27 p.p.m., - H of the methyls in position 2 of the cyclopropane - peak 1.4 - 2.08 p.p.m. - H's of the cyclopropane. Example 50: (1S-trans)-2,2-dimethyl- Ethanol Ethyl (1S-trans)-2,2-dimethyl-3-(2-methyl3-(2-methyl-1-propenyl- 1-propenyl)-cyclopropane-carboxylate. cyclopropane-carboxylic acid
Compounds II Compounds III Compounds I Example 50 (Contd.) NMR spectrum (CDCl3) - peaks at 1.12 and 1.25 p.p.m. - H of the methyls in position 2 of the cyclopropane - peaks at 1.33 - 1.42 p.p.m. - H in position 1 of the cyclopropane - peak at 1.93 to 2.15 p.p.m. - H in position 3 of the cyclopropane - peak at 4.8 - 5.1 p.p.m. - H in position of the propenyl radical. - peak at 1.68 p.p.m. - H of the methyls of the 2-methyl 1-propenyl radical - peaks at 1.12 - 1.25 - 1.38 p.p.m. - H of the ethyl (methyl) - peaks at 3.9 - 4 - 4.1 - 4.2 p.p.m. - H of the CH2 of the ethyl. Example 51: (1R trans)-2,2-dimethyl- Cyclohexanol Cyclohexyl (1R trans)-2,2-dimethyl-3-(2,23-(2,2-difluorovinyl)- -difluorovinyl)-cyclopropane-carboxylate. cyclopropane-carboxylic acid NMR SPECTRUM (CDCl3) - peaks at 1.15 and 1.27 p.p.m. - H of the methyls in position 2 of the cyclopropane - peak at 4.75 p.p.m. - H of the hexyl in position &alpha; of the CO2 - peaks at 3.75 - 3.9 - 4.15 to 4.3 p.p.m. H in position 1 of the difluorovinyl radical.
Compounds II Compounds III Compounds I Example 52: (1R cis)-2,2-dimethyl-3-(2,2- Cyclohexanol Cyclohexyl (1R cis)-2,2-dimethyl-3-(2,2-di -difluorovinyl)-cyclopropane -difluorovinyl)-cyclopropane-carboxylate. carboxylic acid. NMR Spectrum (CDCl3) - peak at 1.22 p.p.m. - H of the methyls of the cyclopropane - peak at 4.67 p.p.m. - H in position &alpha; of the CO2 Example 53: (1S cis)-2,2-dimethyl-3-(2 3-buten-2-ol 3-buten-2-yl (1S cis)-2,2-dimethyl-3-(2-methyl -methyl-1-propenyl)-cyclo- 1-propenyl)-cyclopropane-carboxylate. propane-carboxylic acid [&alpha;]D = -32 # 1 (c = 1.2 % benezene). Example 54: (1R cis)-2,2-dimethyl-3-(2- Crotyl alcohol Crotonyl (1R cis)-2,2-dimethyl-3-(2-methylmethyl-1-propenyl)-cyclo- 1-propenyl)-cyclopropane-carboxylate. propane-carboxylic acid. [&alpha;]D = -37 # 1 (c = 1.7 % benezene).
Example 55: Methyl (1 R cis)-2, 2-dimeth yl-3-(2, 2-dichlorovinyl)-cyclopropane-carboxylate.
21 Cm3 of thionyl chloride is introduced into a solution containing 50 cm3 of hexamethyl phosphotriamide and 60 g of (1 R cis)-2,2-dimethyl-3-(2,2-dichlorvinyl)-cyclopropane-carboxylic acid. The solution obtained is agitated for 2 hours, then, the reaction medium having been taken to 0 C, 12 cm3 of methanol and 50 cm3 of hexamethyl phosphotriamide are introduced, with further agitation for 3 hours at ambient temperature. After pouring into water, then decanting, extracting with diethyl ether and treating the ethereal phases with active carbon, filtering and concentrating to dryness under reduced pressure at 30 C, an oil is obtained which is distilled under a pressure of 0.1 mm of mercury. In this way, 60.84 9 of the product sought is obtained. B.Pt. 66 C.
[a]9 = + 20 + 1 (c = 1.2% benzene) [n]291 1.4945.
Example 56: There are given below the odours given off by some of the compounds with the general formula I.
-Product of example 1: rose odour product of example 4: slightly green note -Product of example 2: green note, minty, -Product of example 3: odour of carnation and rose, floral perfume.
-Product of example 7; orange note.
-Product of example 8: spicy note -Product of example 20: coffee odour, somewhat green -Product of example 9: jasmine - with a hint of apricot -Product of example 10: green note Example 57: Formulations of "Rose" compositions have been prepared, starting with the following ingredients (parts by weight).
-Deterpenated Geranium 180 -Cintronellol 300 -Geranyl acetate 45 -Nerol 15 -Methylionone 15 -Phenylethyl alcohol 1 70 Bourbon Rhodinol 60 Citronellyl acetate 40 Benzoin resinoid 30 -Musk ketone 1 5 -Aldehyde C 9 1/10 PDG 15 -Alpha lonone 1 5 -Product of example 3 100 1000 Example 58: Formulations of "Opoponax" compositions have been prepared, starting with the following ingredients (parts by weight).
-Bergamot 310 -Neroli 131 Fch 20 -Patchouli with iron content removed 10 Rose Essence 10 -Vetiverol 60 -Santanol 125 -Castoreum resinoid 40 -Cumarin 80 -Gamma methylionone 75 -Vanillin 40 Benzoin resinoid 25 -Musk ketone 40 -Musk ambrette 65 -Product of example 9 100 1000 Example 59: Formulations of "Jasmine" compositions have been prepared, starting with the following ingredients (parts by weight).
-lBenzyl acetate 260 -Linalyl acetate 60 -Phenylethyl alcohol 60 -Hexycinnamic aldehyde 90 -Hydroxycitronellal 60 -Benzyl salicylate 50 -Methyl anthranylate 30 -Linalol 45 -Paracresyl phenylacetate 1 5 -Ylang Extra 50 -Santal 30 -Dimethyl Benzyl Carbinol 1 5 -Styrax hyperessence 50 -Hedione 85 -Product of example 9 1 00 1000 Example 60: Example of soaps.
Toilet soaps have been prepared starting with the following ingredients (parts by weight).
Commercial soap paste 1000 -Product of example 9 5 Example 61: Example of detergent powders -Commercial detergent powders 1000 -Product of example 9 1

Claims (33)

1. Compounds of general formula I;
in which R represents a saturated, linear or branched alkyl radical containing from 1 to 12 carbon atoms [optionally substituted by a cycloalkyl radical containing from 3 to 6 carbon atoms or a hydrocarbon chain containing from 2 to 8 carbon atoms (optionally interrupted by an oxygen atom or ketone function)]; a linear or branched, alkyenyl or alkynyl radical containing from 2 to 8 carbon atoms, a cycloalkyl radical containing from 3 to 1 2 carbon atoms (optionally containing one or more double bonds and/or substituted by one or more alkyl radicals); or an optionally substituted aralkyl radical containing from 7 to 1 2 carbon atoms; and R2 and R2 each represents an alkyl radical containing from 1 to 4 carbon atoms or a halogen atom, the said compounds of general formula I being in any one of the possible isomeric forms or mixtures thereof.
2. Compounds as defined in claim 1 in which R represents a linear or branched alkyl radical containing from 1 to 4 carbon atoms.
3. Compounds as defined in claim 1 in which R represents an alkenyl or an alkynyl radical containing from 2 to 6 carbon atoms.
4. Compounds as defined in claim 1 in which R represents a benzyl or a phenyl-ethyl radical.
5. Compounds as defined in any one of claims 1 to 4 in which R2 and R3 are identical.
6. Compounds as defined in claim 5 in which R2 and R3 each represents a methyl radical.
7. Compounds as defined in claim 5 in which R2 and Ra each represents a fluorine or a chlorine atom.
8. 1-Methyl-ethyl (1 R, trans)-2, 2-dimethyl-3-(2-methyl-1 -propenyl)-cyclopropane-carboxylate.
9. Crotonyl (1 R, trans)-2, 2-dimethyl-3-(2-methyl- 1 -propenyl)-cyclopropane-carboxylate.
1 0. 1 -(3-Butenyl) (1 R, trans)-2,2-dimethyl-3-(2-methyl-1 -propenyl)-cyclopropane-carboxylate.
11. 2-Phenyl-ethyl (1 R, trans)-2, 2-dimethyl-3-(2-methyl-1 -propenyl)-cyclopropane-carboxy- late.
1 2. 1-Methyl-ethyl (1 S, trans)-2,2-dimetyl-3-(2-methyl-1-propenyl)-cyclopropane-carboxy- late.
13. (RS) 3-( 1 -Butylene) (1 S, trans)-2,2-dimethyl-3-(2-methyl-1 -propenyl)-cyclopropane-carboxylate.
14. Isopropyl (1 S, cis)-2,2-dimethyl-3-(2-methyl-1 -propenyl)-cyclopropane-carboxylate.
15. 1 -(3-Butenyl) (1 S, cis)-2,2-dimethyl-3-(2-methyl-1-propenyl)-cyclopropane-carboxylate.
16. Methyl (1 R, cis)-2, 2-d imethyl-3-(2, 2-d ifluoro-1 -ethenyl)-cyclopropane-carboxylate.
17. Methyl (1R, cis)-2,2-dimethyl-3-(2,2-dichlorvinyl)-cyclopropane-carboxylate.
18. Compounds as defined in claim 1, other than those claimed in any one of claims 8 to 17, as herein specifically disclosed in any one of Examples 1 to 55.
19. A process for the preparation of compounds as defined in claim 1 which comprises reacting acid of formula II,
(in which R2 and Ra are as defined in claim 1), or a functional derivative of this acid, with an alcohol of formula Ill.
ROH (ill) (in which R is as defined in claim 1), or a functional derivative of this alcohol, whereby the desired compound of formula I is obtained.
20. A process as claimed in claim 19 wherein the acid chloride or anhydride of the acid of formula II is employed.
21. A process as claimed in claim 20 wherein the acid chloride of the acid of formula II is reacted with the alcohol of formula Ill.
22. A process for the preparation of compounds as defined in claim 1 substantially as herein described.
23. A process for the preparation of compounds as defined in claim 1 substantially as herein described in any one of Examples 1 to 55.
24. Compounds as defined in claim 1 whenever prepared by a process as defined in any one of claims 19 to 23.
25. Perfumed compositions containing, as a perfuming agent, at least one compound as defined in claim 1.
26 Compositions as claimed in claim 25 wherein the perfuming agent comprises a compound as defined in any one of claims 2 to 7.
27. Compositions as claimed in claim 25 wherein the perfuming agent comprises a compound as defined in any one of claims 8 to 1 7.
28. Compositions as claimed in any one of claims 25 to 27 in the form suitable for hygienic, cosmetic, disinfectant, maintenance or insecticidal use.
29. Compositions as claimed in any one of claims 25 to 28 in the form of soaps, talcs, shampoos, dentifrices, bath salts, foam baths, bath oils, deodorants, creams, perfumes, cleansing milks, lotions, make-up materials, lip-sticks, nail varnishes, washing solutions or waxes.
30. A method of perfuming an article or composition which comprises incorporating in the said article or composition an effective amount of a compound as claimed in claim 1.
31. As perfuming agents, the compounds of formula I as defined in any one of claims 1 to 7.
32. As perfuming agents, the compounds of formula I as defined in any one of claims 8 to 17.
33. Each and every novel method, process, compound and composition herein disclosed.
GB8129795A 1980-10-03 1981-10-02 Cyclopropane carboxylic acid derivatives Expired GB2087384B (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
FR8021216A FR2491461B1 (en) 1980-10-03 1980-10-03 NOVEL DERIVATIVES OF CYCLOPROPANE CARBOXYLIC ACID, PROCESS FOR THEIR PREPARATION AND THEIR APPLICATION TO THE PREPARATION OF PERFUMING COMPOSITIONS

Publications (2)

Publication Number Publication Date
GB2087384A true GB2087384A (en) 1982-05-26
GB2087384B GB2087384B (en) 1985-07-17

Family

ID=9246531

Family Applications (1)

Application Number Title Priority Date Filing Date
GB8129795A Expired GB2087384B (en) 1980-10-03 1981-10-02 Cyclopropane carboxylic acid derivatives

Country Status (7)

Country Link
JP (1) JPS57131743A (en)
CH (1) CH651010A5 (en)
DE (1) DE3139300A1 (en)
FR (1) FR2491461B1 (en)
GB (1) GB2087384B (en)
IT (1) IT1171563B (en)
NL (1) NL8104495A (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2023036439A1 (en) * 2021-09-13 2023-03-16 Symrise Ag Cyclopropanated fragrance compounds

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CH610868A5 (en) * 1975-09-12 1979-05-15 Inventio Ag Pipe-burst safety device arranged directly at the outlet of the cylinder of a hydraulic lift

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2023036439A1 (en) * 2021-09-13 2023-03-16 Symrise Ag Cyclopropanated fragrance compounds

Also Published As

Publication number Publication date
GB2087384B (en) 1985-07-17
NL8104495A (en) 1982-05-03
IT8149410A0 (en) 1981-10-01
FR2491461A1 (en) 1982-04-09
FR2491461B1 (en) 1985-08-23
JPS57131743A (en) 1982-08-14
DE3139300A1 (en) 1982-06-16
CH651010A5 (en) 1985-08-30
IT1171563B (en) 1987-06-10

Similar Documents

Publication Publication Date Title
JP5563454B2 (en) Cyclohexene derivatives and their use as odorants
CH653668A5 (en) DERIVATIVES OF CYCLOPROPANE, THEIR PREPARATION PROCESS, PERFUMING AGENTS CONSISTING OF THE SAME AND PERFUMING COMPOSITIONS CONTAINING THEM.
JP2007536285A (en) Cycloaliphatic carboxylic acid oxycarbonylmethyl esters and their use as odorants
JP3352849B2 (en) Perfume compositions or perfumed products, methods for conferring, improving, increasing or modifying odor properties, and cyclic diesters
JP4909351B2 (en) Α-Decalon with Damascon&#39;s woody smell
JP5689135B2 (en) Esters as perfuming ingredients
JP4352002B2 (en) Esters and their use in fragrances
RU2482108C2 (en) Substituted octan(ene)nitriles, method for production thereof and use thereof in perfumery
JP4416186B2 (en) Fragrance containing 3-alkylcycloalkanols
JP4012461B2 (en) Unsaturated ester compounds, their use and perfumed compositions and perfumed products containing them
JP5355698B2 (en) Chemically stable ingredient for lemon flavoring
JP2022509417A (en) Alkoxybenzaldehyde derivatives and their precursors
MX2014008863A (en) Aldehydes as perfuming ingredients.
JP2010512347A (en) Cyclohexenyl butenones and fragrance compositions containing them
US6177400B1 (en) Unsaturated ketones and their use in perfumery
GB2087384A (en) Cyclopropane carboxylic acid derivatives
JP2019532123A (en) Organic compounds
US4406829A (en) Novel cyclopropane carboxylate esters
EP2622051B1 (en) 4,4-dimethyl-decal-1-one or -1-ol derivatives as perfuming ingredients
FR3030520A1 (en) NOVEL ACETALS OF 1- (3,3-DIMETHYLCYCLOHEX-1-ENYL) ETHANONE, PROCESS FOR THEIR PREPARATION AND THEIR USE IN PERFUMERY
US7129206B2 (en) Utilization of unsaturated esters as perfuming ingredients
FR2543134A2 (en) New cyclopropane derivatives, process for their preparation and their application to the preparation of perfuming compositions
GB2091727A (en) Derivatives of cyclopropane carboxylic acid, their preparation, their use as perfuming agents and compositions containing them
JP2007507434A (en) 3-Isopropyl-1-methylcyclopentyl derivatives and their use in fragrance products
WO2013170976A1 (en) Organic compounds

Legal Events

Date Code Title Description
PCNP Patent ceased through non-payment of renewal fee