EP0215799B1 - Tricyclo [5.2.1.0/2,6] decan/decen-derivate mit funktionalisierter alkyliden-seitenkette und deren verwendung als riechstoffe - Google Patents

Tricyclo [5.2.1.0/2,6] decan/decen-derivate mit funktionalisierter alkyliden-seitenkette und deren verwendung als riechstoffe Download PDF

Info

Publication number
EP0215799B1
EP0215799B1 EP86900063A EP86900063A EP0215799B1 EP 0215799 B1 EP0215799 B1 EP 0215799B1 EP 86900063 A EP86900063 A EP 86900063A EP 86900063 A EP86900063 A EP 86900063A EP 0215799 B1 EP0215799 B1 EP 0215799B1
Authority
EP
European Patent Office
Prior art keywords
exo
endo
derivatives
tricyclo
unsaturated
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.)
Expired
Application number
EP86900063A
Other languages
German (de)
English (en)
French (fr)
Other versions
EP0215799A1 (de
Inventor
Ernst-Joachim Brunke
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.)
Dragoco Gerberding and Co GmbH
Original Assignee
Dragoco Gerberding and Co GmbH
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 Dragoco Gerberding and Co GmbH filed Critical Dragoco Gerberding and Co GmbH
Publication of EP0215799A1 publication Critical patent/EP0215799A1/de
Application granted granted Critical
Publication of EP0215799B1 publication Critical patent/EP0215799B1/de
Expired legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11B—PRODUCING, e.g. BY PRESSING RAW MATERIALS OR BY EXTRACTION FROM WASTE MATERIALS, REFINING OR PRESERVING FATS, FATTY SUBSTANCES, e.g. LANOLIN, FATTY OILS OR WAXES; ESSENTIAL OILS; PERFUMES
    • C11B9/00—Essential oils; Perfumes
    • C11B9/0061—Essential oils; Perfumes compounds containing a six-membered aromatic ring not condensed with another ring

Definitions

  • GB-OS 2020277 describes the aldol condensation of this aldehyde 3 with aliphatic aldehydes which lead to the unsaturated tricyclodecene-aldehydes 4 in the side chain with the exo arrangement of the functionalized ones Side chain and endo link at C-2 and C-6 leads, the dashed line means an optional double bond at C-4.
  • These aldehydes 4 have odor notes from Wood type with secondary notes of iris root and honey and can be used as fragrances.
  • the tricyclodecane / decene derivatives according to the general formula A with a functionalized alkylidene side chain are new and nothing has been known about their olfactory properties.
  • the aldehydes and ketones covered by this formula A differ fundamentally from all known aldehydes and ketones in that they are ⁇ , Y-unsaturated with respect to the carbonyl group, that is to say the CC double bond in the side chain is deconjugated to the carbonyl group and no longer, as in the known compounds, is conjugated.
  • the associated shift of the double bond in the side chain is the same for the associated primary and secondary alcohols.
  • the derivatives A according to the invention are notable for high stability compared to the known compounds.
  • the known aldehydes and ketones are both sensitive to acid and sensitive to oxidation, which is probably related to the fact that the known aldehydes and ketones are to be regarded as the direct reaction product of an aldol condensation and the aldol condensation is a normally reversible reaction, i.e. is in equilibrium with an aldol cleavage.
  • the aldehydes and ketones according to the formula A according to the invention are not a direct reaction product of an aldol condensation and are also not subject to the aldol cleavage.
  • the derivatives A according to the invention also meet all other requirements for a fragrance. They can be produced inexpensively with constant quality, and their fragrance notes are also very intense and are such that an addition of relatively small amounts of the derivatives A z according to the invention is already possible. B. to perfume oils has a significantly improving effect. Overall, the derivatives A according to the invention thus represent very valuable odoriferous substances. In addition, however, they are also well suited as aroma substances or as constituents of aroma concentrates for foodstuffs and luxury foods or animal feeds.
  • the ⁇ , ⁇ -unsaturated aldehydes or ketones with the same substituents R 1 and R 2 and R a to R d are expediently used, some of which are known or can be prepared analogously to the known compounds.
  • acidic catalysts preferably adipic acid
  • favored by increasing the temperature e.g. with slow vacuum distillation in the presence of adipic acid
  • the ring system of the derivatives A according to the invention may be unsaturated or saturated, may have additional methyl substituents and may also be in the endo form or exo form.
  • the tricyclodecene derivatives unsaturated and not methyl-substituted in the ring system according to formula A are prepared starting from the unsaturated tricyclodecene aldehyde 8, which in a known manner from endodicyclopentadiene (endo-1) or exodicyclopentadiene (exo-1) is formed by selective hydroformylation and is used either in its endo form (endo-8) or in its exo form (exo-8).
  • the aldehyde endo-8 and exo-8 are aldol condensed with lower aliphatic Aldehydes or ketones form the ⁇ , ⁇ -unsaturated derivatives endo-9 or exo-9, which are converted into the aldehydes or ketones endo-10 or exo-10 according to the invention by deconjugation.
  • the aldehydes or ketones endo-10 or exo-10 can optionally be reduced to the primary or secondary alcohols endo-11 or exo-11, which are also according to the invention.
  • the hydroformylation of the dicyclopentadiene endo-1 or exo-1 can also be carried out in such a way that instead of the aldehyde 8 unsaturated in the ring system, the tricyclodecane aldehyde 7 saturated in the ring system is formed.
  • This saturated aldehyde 7, which is also used again in its endo form or in its exo form can be condensed analogously to the aldehyde 8 to the ⁇ , ⁇ -unsaturated carbonyl compounds 12, from which the ⁇ , Y-unsaturated carbonyl compounds according to the invention are formed by deconjugation, which in turn, if necessary, reduces them to the ⁇ , y-unsaturated alcohols 14 likewise according to the invention will.
  • the non-methyl-substituted tricyclodecane derivatives which are saturated in the ring system can be prepared in accordance with the formula A.
  • methyl-substituted dicyclopentadiene is obtained by selective hydroformylation either in the methylated and unsaturated tricyclodecene aldehyde 15 in the ring system or in the methylated and in the ring system saturated tricyclodecane aldehyde 19 implemented.
  • the a, ⁇ -unsaturated carbonyl compounds 16 or 20 can be prepared by aldol condensation, from which the ⁇ , Y-unsaturated carbonyl compounds 17 or 21 according to the invention are obtained by deconjugation and the ⁇ , vT-unsaturated alcohols 18 or 22 likewise according to the invention are subsequently obtained .
  • the derivatives 13, 14, 17, 18, 21 and 22 according to the invention are, as has been described for the derivatives 10 and 1.1, in their endo form or in their exo form, depending on whether the ( possibly methyl-substituted) dicyclopentadiene was used in the endo form or the exo form.
  • all derivatives A according to the invention have, in addition to this predetermined 2,6-endo / exo isomerism, also a cis / trans isomerism on the ⁇ , Y-permanent double bond (9,1'-Z and 9,1 '-E), whereby it depends on the conditions of the individual case whether during deconjugation essentially only one of the cis / trans isomers is formed or both of these isomers are obtained.
  • the cis / trans isomers of the derivatives A according to the invention have similar and valuable smell properties, whereas the 2,6-endo / exo isomers of the same C-9 substitution differ in smell from one another, as is also the case with the known a, ⁇ -unsaturated ones Compounds of the same C-9 substitution were observed. Otherwise, the 2,6-endo / exo isomers of the same C-9 substitution also differ in each case in their gas-chromatic retention behavior, while their IR spectra, 1 H-NMR spectra and mass spectra are each very similar.
  • Table 1 shows some of the derivatives for the production of the derivatives according to the invention
  • Formula A is compiled into the lower aliphatic aldehydes or ketones used in the aldol condensation, and at the same time the particular type of substitution that results in each case (ie the specifically resulting substituents R 1 and R 2 ) is indicated.
  • the ketone exo-9c obtained according to Example 3a was mixed with 1 g of adipic acid and stirred for 1 hour at 60 ° C. under a nitrogen atmosphere. Partial deconjugation occurred.
  • Mass spectrum (main peak): m / z (%) 230 (4, M + ), 164 (46), 159 (21), 144 (6), 117 (8), 93 (62), 77 (26).
  • Mass spectrum (main peak): m / z (%) 218 (M + , 11), 203 (2), 173 (26), 152 (12), 145 (5), 134 (10), 131 (11), 119 (10), 117 (9), 108 (45), 107 (100), 91 (72), 81 (55), 79 (73), 67 (85).
  • This perfume oil has a fresh, spicy fragrance with distinctive lavender aspects.
  • 70 parts of the ketone exo-1 Oc are added, a new, spicy-herb fragrance complex is created with great harmony and charisma.
  • the fruity-woody character of this mixture is rounded off by adding 150 parts of the alcohol exo-11 d in a very desired manner, with a soft-woody tonality occurring at the same time.
  • the alternative addition of 150 parts of the alcohol endo-11 d also results in a rounding-off, whereby at the same time a soft, flowery tonality emerges.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Fats And Perfumes (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Cosmetics (AREA)
EP86900063A 1984-12-19 1985-12-16 Tricyclo [5.2.1.0/2,6] decan/decen-derivate mit funktionalisierter alkyliden-seitenkette und deren verwendung als riechstoffe Expired EP0215799B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE3446232 1984-12-19
DE3446232 1984-12-19

Publications (2)

Publication Number Publication Date
EP0215799A1 EP0215799A1 (de) 1987-04-01
EP0215799B1 true EP0215799B1 (de) 1988-08-24

Family

ID=6253148

Family Applications (1)

Application Number Title Priority Date Filing Date
EP86900063A Expired EP0215799B1 (de) 1984-12-19 1985-12-16 Tricyclo [5.2.1.0/2,6] decan/decen-derivate mit funktionalisierter alkyliden-seitenkette und deren verwendung als riechstoffe

Country Status (4)

Country Link
EP (1) EP0215799B1 (https=)
JP (1) JPS62501149A (https=)
DE (1) DE3564564D1 (https=)
WO (1) WO1986003737A1 (https=)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE10144816A1 (de) * 2001-09-12 2003-03-27 Dragoco Gerberding Co Ag Duft-und Aromastoff
US10767004B1 (en) 2020-01-13 2020-09-08 Dairen Chemical Corporation Tricyclodecane dimethanol composition and uses thereof

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR1416209A (fr) * 1964-04-16 1965-10-29 Norda Essential Oil & Chemical Dérivés oxygénés de dicyclodiène
US4057515A (en) * 1969-02-04 1977-11-08 N.V. Chemische Fabriek "Naarden" Perfume compositions
JPS6039256B2 (ja) * 1978-05-04 1985-09-05 花王株式会社 三環式α，β−不飽和アルデヒド
JPS54148768A (en) * 1978-05-10 1979-11-21 Kao Corp Novel tricyclic alpha,beta-unsaturated ketone
DE3303893C2 (de) * 1983-02-05 1985-01-24 Dragoco Gerberding & Co Gmbh, 3450 Holzminden 2,6-Exo-konfigurierte Tricyclo[5.2.1.0↑2↑↑,↑↑6↑]decan-Derivate mit funktionalisierter Seitenkette an C-9 und ihre Verwendung als Riechstoffe

Also Published As

Publication number Publication date
JPS62501149A (ja) 1987-05-07
JPH0471895B2 (https=) 1992-11-16
EP0215799A1 (de) 1987-04-01
DE3564564D1 (en) 1988-09-29
WO1986003737A1 (fr) 1986-07-03

Similar Documents

Publication Publication Date Title
DE2718549A1 (de) Neue riechstoffe
DE69729809T2 (de) Cyclopentanbutanolderivate
DE2405568A1 (de) Cycloaliphatische verbindungen, deren herstellung und verwendung
CH633508A5 (de) Verfahren zur herstellung von neuen cycloaliphatischen gesaettigten und ungesaettigten ketonen, die als aroma- und duftstoffe brauchbar sind.
DE2163868A1 (de) Verfahren zur Herstellung gamma, deltaungesättigter Carbonylderivate
DE2812583C2 (de) 2,4,4-Trimethyl-3-[but(-2-en; -1,3-dien)yl]-cyclohex-2-en-1-one, Verfahren zu deren Herstellung und sie enthaltende Riech- und Geschmackstoffkompositionen
DE69108314T2 (de) Dihydro-Campholen-Aldehydderivate.
EP0252378B1 (de) Neue aliphatische Aldehyde, Verhahren zu deren Herstellung und deren Verwendung als Riechstoffe
DE2559751C2 (de) Verwendung einer Spiranverbindung als Riech- bzw. Aromastoff
DE2756772C2 (https=)
EP0215799B1 (de) Tricyclo [5.2.1.0/2,6] decan/decen-derivate mit funktionalisierter alkyliden-seitenkette und deren verwendung als riechstoffe
DE2159924B2 (de) Jonon- und ironderivate, verfahren zu ihrer herstellung und riech- und/oder geschmackstoffkompositionen
EP0002510A1 (de) Cyclohexane, Verfahren zu deren Herstellung, deren Verwendung und diese enthaltende Kompositionen
EP0684299A2 (de) Dihydrofarnesal
EP0000719A2 (de) Neue 1,4-Epoxy-trimethyl-butenyliden-cyclohexane (I), Verfahren zu deren Herstellung, Verwendung von (I) als Riech- und/oder Geschmackstoffe, Riech- und/oder Geschmackstoffkompositionen mit einem Gehalt an den neuen Cyclohexanen
EP0203152B1 (de) Methylsubstituierte bicyclo ad2.2.1 bdheptan-nitrile, verfahren zur herstellung dieser nitrile und deren verwendung als riechstoffe
CH624844A5 (en) Odoriferous composition
EP0533892B1 (de) 8-exo-formyl-2,6-exo-tricyclo[5.2.1.0/2,6]decan, verfahren zu seiner herstellung sowie verwendung desselben
EP0195975A2 (de) Bicyclisches Keton, Verfahren zu dessen Herstellung und Riech- und/oder Geschmackstoffkompositionen mit einem Gehalt an diesem bicyclischen Keton
DE3205320A1 (de) Verwendung von (alpha)-trans-bergamotol-derivaten als riech- und aromastoffe
DE3245047A1 (de) Aliphatische alkohole und ester und ihre verwendung als parfumbestandteile
DE2163521A1 (https=)
DE3128790A1 (de) C-8-substituierte 1,5-dimethyl-bicyclo (3.2.1)octan-8-ole
EP0011877B1 (de) Neue Caranderivate (I), Verfahren zu deren Herstellung, Verwendung von I als Riechstoffe sowie Riechstoffkompositionen mit einem Gehalt an I.
DE2707340A1 (de) Verfahren zur herstellung neuer gemische und aus diolen bestehender zwischenprodukte

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): CH DE FR GB LI NL

17P Request for examination filed

Effective date: 19861206

17Q First examination report despatched

Effective date: 19871008

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): CH DE FR GB LI NL

GBT Gb: translation of ep patent filed (gb section 77(6)(a)/1977)
REF Corresponds to:

Ref document number: 3564564

Country of ref document: DE

Date of ref document: 19880929

RTI2 Title (correction)

Free format text: TRICYCLO (5.2.1.0/2,6) DECANE/DECENE DERIVATIVES WITH FUNCTIONALIZED ALKYLIDENE SIDE CHAINS AND UTILIZATION THEREOF AS PERFUMING SUBSTANCES.

R20 Corrections of a patent specification

Effective date: 19880930

ET Fr: translation filed
PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

26N No opposition filed
PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: NL

Payment date: 19921231

Year of fee payment: 8

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: CH

Payment date: 19930118

Year of fee payment: 8

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LI

Effective date: 19931231

Ref country code: CH

Effective date: 19931231

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: NL

Effective date: 19940701

NLV4 Nl: lapsed or anulled due to non-payment of the annual fee
REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: FR

Payment date: 19941229

Year of fee payment: 10

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: GB

Payment date: 19941230

Year of fee payment: 10

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: DE

Payment date: 19950224

Year of fee payment: 10

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GB

Effective date: 19951216

GBPC Gb: european patent ceased through non-payment of renewal fee

Effective date: 19951216

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: FR

Effective date: 19960830

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: DE

Effective date: 19960903

REG Reference to a national code

Ref country code: FR

Ref legal event code: ST