[go: up one dir, main page]

WO1993010068A1 - Derives du butenol, leur fabrication et leur application - Google Patents

Derives du butenol, leur fabrication et leur application Download PDF

Info

Publication number
WO1993010068A1
WO1993010068A1 PCT/EP1992/002611 EP9202611W WO9310068A1 WO 1993010068 A1 WO1993010068 A1 WO 1993010068A1 EP 9202611 W EP9202611 W EP 9202611W WO 9310068 A1 WO9310068 A1 WO 9310068A1
Authority
WO
WIPO (PCT)
Prior art keywords
methyl
trimethyl
compounds
cyclopenten
radical
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.)
Ceased
Application number
PCT/EP1992/002611
Other languages
German (de)
English (en)
Inventor
Thomas Markert
Volker Porrmann
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.)
Henkel AG and Co KGaA
Original Assignee
Henkel AG and Co KGaA
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 Henkel AG and Co KGaA filed Critical Henkel AG and Co KGaA
Publication of WO1993010068A1 publication Critical patent/WO1993010068A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C49/00—Ketones; Ketenes; Dimeric ketenes; Ketonic chelates
    • C07C49/20—Unsaturated compounds containing keto groups bound to acyclic carbon atoms
    • C07C49/21—Unsaturated compounds containing keto groups bound to acyclic carbon atoms containing rings other than six-membered aromatic rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C33/00—Unsaturated compounds having hydroxy or O-metal groups bound to acyclic carbon atoms
    • C07C33/05—Alcohols containing rings other than six-membered aromatic rings
    • C07C33/12—Alcohols containing rings other than six-membered aromatic rings containing five-membered rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
    • C07C45/67—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton
    • C07C45/68—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms
    • C07C45/72—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms by reaction of compounds containing >C = O groups with the same or other compounds containing >C = O groups
    • C07C45/74—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms by reaction of compounds containing >C = O groups with the same or other compounds containing >C = O groups combined with dehydration
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C47/00—Compounds having —CHO groups
    • C07C47/20—Unsaturated compounds having —CHO groups bound to acyclic carbon atoms
    • C07C47/225—Unsaturated compounds having —CHO groups bound to acyclic carbon atoms containing rings other than six-membered aromatic rings

Definitions

  • the invention relates to new butenol derivatives, a process for their preparation and their use as fragrances.
  • sandalwood oil is particularly valued and valuable. It is obtained from the heartwood of sandalwood, a tropical semi-parasite found in India and Malaysia, by steam distillation. Heartwood appears after about ten years and only begins to develop more quickly in twenty-year-old trees. Fully grown trees are cleared at the age of 30 to 60 years because the roots are particularly rich in fragrant heartwood [cf. E. T. Morris, Dragoco Report 1983 (30), 40]. It is therefore understandable that fragrance research is constantly striving to develop suitable substitutes for natural sandalwood oil.
  • RENaipawer outlined the focal points in the development of suitable substitutes for natural sandalwood oil in a review [in: BMLawrence, BDMookherjee, BJWillis (ed.): "Flavors and Fragrances: A World Perspective”; Elsevier Publishers, Amsterdam 1988].
  • Alcohols with a 2,2,3-trimethyl-3-cyclopentenyl group are known from European patent EP 155 591 B1. However, this group contains a side chain which is either saturated or has a double bond in position.
  • the US patent US 4,052,341 relates to 3-methyl-5- (2,2 r 3-trimethyl-3-cyclopenten-l-yl) pentan-2-ol.
  • fragrance industry has a constant need for new fragrances with interesting fragrance notes in order to supplement the range of naturally available fragrances and to make the necessary adaptations to changing fashionable tastes and the constantly increasing demand of odor improvers for everyday products such as cosmetics and cleaning agents.
  • radical Rl is hydrogen or an alkyl group having 1 to 4 carbon atoms and the radical R 2 is an alkyl group having 1 to 4 carbon atoms, with the meaning of a methyl group being excluded for R 2 if Rl is a methyl group.
  • Those compounds of the general formula (I) according to the invention are particularly preferred in which the radical R 1 is hydrogen, methyl or ethyl and the radical R 2 is methyl, ethyl, propyl or isopropyl.
  • 4-Methyl-6- (2,2,3-trimethyl-3-cyclopenten-l-yl) 4-hexen-3-ol, 4-ethyl-6- (2,2,3-trimethyl) are very particularly preferred -3-cyclopenten-l-yl) -4-hexen-3-o and 2,4-dimethyl-6- (2,2,3-trimethyl-3-cyclopenten-l-yl) 4-hexen-3-ol .
  • Another object of the invention is a process for the preparation of butenol derivatives of the general formula (I), in which R 1 and R 2 have the meaning given above, by condensation of ⁇ -campholenaldehyde with the corresponding aldehydes or ketones to give the corresponding unsaturated compounds Carbonyl compounds and subsequent reduction of the carbonyl function of these compounds z.
  • the new compounds (I) are prepared by known synthetic organic chemical processes.
  • the starting material is ⁇ campholenaldehyde, which can be reacted in the presence of conventional catalysts with corresponding short-chain aldehydes and ketones, for example 2-butano or 3-pentanone, in a mixed aldol condensation, with the corresponding ⁇ , ß-unsaturated compounds being eliminated directly via intermediate aldol condensation products Aldol condensation products are obtained.
  • the reaction is expediently carried out with an excess de more reactive and volatile components.
  • suitable catalysts are sodium hydroxide, sodium ethanolate, sodium id, potassium tert-butoxide or heterogeneous catalysts such as potassium fluoride on aluminum oxide.
  • the carbonyl function of the aldol condensation products can be reduced to the OH group in a further reaction, for example by means of complex hydrides such as lithium aluminum hydride or lithium or sodium borohydride. In this way, the butenol derivatives of the general formula (I) are obtained.
  • the compounds (I) can then be purified by customary methods, for example by distillation.
  • the compounds (I) according to the invention have remarkable odor properties. Another object of the invention is therefore the use of the compounds of general formula (I) as fragrances.
  • the compounds (I) and in particular 4-methyl-6- (2,2,3-trimethyl-3-cyclopenten-l-yl) -4-hexen-3-ol are distinguished by their sandal scent with very complex shades and large Charisma.
  • the odor profile of the compounds (I) is original and novel compared to the prior art mentioned.
  • the odor intensity of the compounds (I) is higher than that of the closest prior art;
  • the compounds (I) enhance the harmony and charisma as well as the adhesion, the dosage being matched to the desired fragrance note, taking into account the other constituents of the composition.
  • the compounds of the formula (I) are particularly suitable for modifying and enhancing known compositions. Particularly to be emphasized is their extraordinary olfactory strength, which generally contributes to the refinement of the composition.
  • the compounds of formula (I) can be used with numerous known fragrance ingredients, e.g. combine other fragrances of natural, synthetic or partially synthetic origin, essential oils and plant extracts.
  • the range of natural fragrances can include both volatile, medium and low volatile components and that of synthetic fragrances includes representatives from practically all classes of substances. Examples are:
  • Natural products such as tree moss absolute, basil oil, agricultural oils such as bergamot oil, mandarin oil, etc., mastic absolute, myrtle oil, pal arosa oil, patchouli oil, petitgrain oil, Wer utöl, myrrh oil, olibanum oil
  • aldehydes such as citral, helional ⁇ , ⁇ -hexylcinnamaldehyde, hydroxycitronellal, lilial R [p-tert.-butyl- ⁇ -methyldihydrocinnamaldehyde], methylnonyl acetaldehyde,
  • ketones such as allyl ionone, ionone, ⁇ -ionone, isoraldein, methyl ionone,
  • esters such as allylphenoxyacetate, benzyl salicylate, cinnamyl propionate, citronellyl acetate, citronellyl ethoxylate, decyl acetate, dimethylbenzylcarbyl acetate, ethyl acetoacetate, hexenyl isobutyrate, linalyl acetate, methyl dihydrojasyl acetate, cyclohexyl acetate, vetyl hexyl acetate
  • Lactones such as gamma-undecalactone, l-0xaspiro [4.4] nonan-2-one, as well as various other components often used in perfumery such as ketone musk, indole, p-menthan-8-thiol-3-one, methyleugenol, ambroxan .
  • the compounds according to the invention contain centers of chirality, so that these compounds can exist in different spatial forms.
  • the compounds according to the invention are obtained as mixtures of the corresponding isomers and are used as such as fragrances.
  • the usable proportions of the compounds according to the invention or their mixtures in fragrance compositions range from 1 to 70 percent by weight, based on the mixture as a whole.
  • Mixtures of the compounds (I) according to the invention and compositions of this type can be used both for perfuming cosmetic preparations such as lotions, creams, sha poos, soaps, ointments, powders, aerosols, toothpastes, mouthwashes, deodorants and in alcoholic perfumery (eg Eaux de Cologne, Eaux de Toilette, extras) can be used.
  • perfuming technical products such as detergents and cleaning agents, fabric softeners and textile treatment agents or tobacco.
  • compositions are added to them in an olfactory effective amount, in particular in a concentration of 0.05 to 2 percent by weight, based on the entire product.
  • these values are not intended to represent any limit values, since the experienced perfumer can achieve effects with even lower concentrations or build new types of complexes with even higher doses.
  • Example 1 4-methyl-6- (2, 2, 3-trimethyl-3-cyclopenten-l-yl) -4-hexen-3-one
  • Example 5 4-ethyl-6- (2,2,3-trimethyl-3-cyclopenten-l-yl) -4-hexen-3-ol
  • 11.2 g (0.1 4 mol) of magnesium shavings are covered with 100 ml of anhydrous ether and 49.7 g (0.46 mol) of ethyl bromide are slowly metered in with stirring over the course of 40 minutes.
  • 72 g of 2-ethyl-4- (2,2,3-trimethyl-3-cyclopenten-l-yl) -2-buten-l-al (Example 2) were subsequently added to the resulting solution of the Grignard reagent within 90 Dripped minutes.
  • the odor intensity of the compounds according to the invention was determined in comparison with 3-methyl-5- (2,2,3-trimethyl-3-cyclopenten-l-yl) pentan-2-ol.
  • solutions of the odoriferous substances to be investigated were prepared in dipropylene glycol and diluted in each case until an odor could just be perceived; the minimum concentration determined in this way by a panel of 16 test persons for the perception of the smell of the respective fragrance is referred to as the odor threshold.
  • the concentration for the odor threshold value determined for Comparative Example 1 was designated as 1.0 and the values of Examples 3 to 6 according to the invention based on this.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Fats And Perfumes (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Cosmetics (AREA)

Abstract

L'invention concerne des dérivés du buténol de formule générale (I) dans laquelle R1 représente hydrogène ou un groupe alkyle de 1 à 4 atomes de carbone et le reste R2 un groupe alkyle de 1 à 4 atomes de carbone, à condition que R2 ne représente pas un groupe méthyle si R1 représente un groupe méthyle. Ces composés sont des parfums à notes intéressantes et d'exhalaison prononcée.
PCT/EP1992/002611 1991-11-22 1992-11-13 Derives du butenol, leur fabrication et leur application Ceased WO1993010068A1 (fr)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
DE4138437 1991-11-22
DEP4138437.7 1991-11-22
DE19924203790 DE4203790A1 (de) 1991-11-22 1992-02-10 Butenol-derivate, deren herstellung und verwendung
DEP4203790.5 1992-02-10

Publications (1)

Publication Number Publication Date
WO1993010068A1 true WO1993010068A1 (fr) 1993-05-27

Family

ID=25909387

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP1992/002611 Ceased WO1993010068A1 (fr) 1991-11-22 1992-11-13 Derives du butenol, leur fabrication et leur application

Country Status (2)

Country Link
DE (1) DE4203790A1 (fr)
WO (1) WO1993010068A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2236487A2 (fr) 2009-04-02 2010-10-06 International Flavors & Fragrances Inc. Procédé de production de levosandal et de levosandol

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4173585A (en) * 1978-08-10 1979-11-06 International Flavors & Fragrances Inc. 2,2,3-Trimethyl-3-cyclopenten-1-ylalkenyl- and alkylidene-cycloalkanones

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4173585A (en) * 1978-08-10 1979-11-06 International Flavors & Fragrances Inc. 2,2,3-Trimethyl-3-cyclopenten-1-ylalkenyl- and alkylidene-cycloalkanones

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2236487A2 (fr) 2009-04-02 2010-10-06 International Flavors & Fragrances Inc. Procédé de production de levosandal et de levosandol

Also Published As

Publication number Publication date
DE4203790A1 (de) 1993-05-27

Similar Documents

Publication Publication Date Title
EP0636116B1 (fr) Derives de pentene, leur fabrication et utilisation
EP1280763B1 (fr) Composes trimethyldecene
EP1284951B1 (fr) Derives de 3,3-dimethylcyclohexane
WO1993010068A1 (fr) Derives du butenol, leur fabrication et leur application
EP1296918B1 (fr) Dérivés de diméthylbenzène en tant qu'agents parfumants
EP0975570B1 (fr) Cetals de phenone et leur utilisation comme substances odoriferantes
WO1993003001A1 (fr) Derives de trimethylhexanal, leur preparation et leur utilisation
DE4131119A1 (de) Hexen-derivate, deren herstellung und verwendung
EP0863864B1 (fr) Composes carbonyle
DE10022971B4 (de) Verwendung von 4-(2,2,3-Trimethylcyclopentan-1-yl)-2-methylbutanal als Riechstoff
EP1129060B1 (fr) Composes carbonyle et leur utilisation comme parfums
DE4415690A1 (de) Aromatische Carbonylverbindungen
EP1476527B1 (fr) Utilisation de derives d'hexenal comme parfums
EP0586442B1 (fr) Utilisation de derives isomeres 1,1,1-trialkyl-2-phenyl-ethane comme parfums, et compositions de parfums renfermant ces derives
WO1993002998A1 (fr) Composes bicycliques, leur preparation et leur utilisation
EP1485350B1 (fr) Utilisation de cetones insaturees en tant que substances odorantes
DE19521364A1 (de) Cyclohexyl-substituierte Alkanole
DE4304467A1 (de) Hexanol-Derivate, deren Herstellung und Verwendung
WO1994018150A1 (fr) Derives d'hexanone, leur preparation et leur utilisation
WO1996025382A1 (fr) Produits de condensation
DE19520556A1 (de) Aromatische Carbonylverbindungen

Legal Events

Date Code Title Description
AK Designated states

Kind code of ref document: A1

Designated state(s): JP US

AL Designated countries for regional patents

Kind code of ref document: A1

Designated state(s): AT BE CH DE DK ES FR GB GR IE IT LU MC NL SE

DFPE Request for preliminary examination filed prior to expiration of 19th month from priority date (pct application filed before 20040101)
122 Ep: pct application non-entry in european phase