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DE2753644C2 - Cyclopentane derivatives, process for their preparation and their use - Google Patents

Cyclopentane derivatives, process for their preparation and their use

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Publication number
DE2753644C2
DE2753644C2 DE19772753644 DE2753644A DE2753644C2 DE 2753644 C2 DE2753644 C2 DE 2753644C2 DE 19772753644 DE19772753644 DE 19772753644 DE 2753644 A DE2753644 A DE 2753644A DE 2753644 C2 DE2753644 C2 DE 2753644C2
Authority
DE
Germany
Prior art keywords
cyclopentane derivatives
preparation
alkyl radical
formula
catalyst
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
DE19772753644
Other languages
German (de)
Other versions
DE2753644A1 (en
Inventor
Robin Thomas Gray
Aaldert Johannes De Amsterdam Jong
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.)
Shell Internationale Research Maatschappij BV
Original Assignee
Shell Internationale Research Maatschappij BV
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 Shell Internationale Research Maatschappij BV filed Critical Shell Internationale Research Maatschappij BV
Publication of DE2753644A1 publication Critical patent/DE2753644A1/en
Application granted granted Critical
Publication of DE2753644C2 publication Critical patent/DE2753644C2/en
Expired legal-status Critical Current

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Classifications

    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11BPRODUCING, 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
    • C11B9/00Essential oils; Perfumes
    • C11B9/0026Essential oils; Perfumes compounds containing an alicyclic ring not condensed with another ring
    • C11B9/003Essential oils; Perfumes compounds containing an alicyclic ring not condensed with another ring the ring containing less than six carbon atoms
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C35/00Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a ring other than a six-membered aromatic ring
    • C07C35/02Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a ring other than a six-membered aromatic ring monocyclic
    • C07C35/06Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a ring other than a six-membered aromatic ring monocyclic containing a five-membered rings
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/49Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reaction with carbon monoxide
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C47/00Compounds having —CHO groups
    • C07C47/02Saturated compounds having —CHO groups bound to acyclic carbon atoms or to hydrogen
    • C07C47/19Saturated compounds having —CHO groups bound to acyclic carbon atoms or to hydrogen containing hydroxy groups
    • C07C47/192Saturated compounds having —CHO groups bound to acyclic carbon atoms or to hydrogen containing hydroxy groups containing rings

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Fats And Perfumes (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)

Description

Die Erfindung betrifft neue Cyclopentan-Derivate, die als chemische Aromastoffe von Interesse sind, Verfahren zu ihrer Herstellung und ihre Verwendung für parfümierte Produkte.The invention relates to new cyclopentane derivatives which are of interest as chemical flavorings, processes for their manufacture and their use in perfumed products.

In der DE-OS 27 35 639 sind Cyclohexan-Derivate der Formel I beschriebenIn DE-OS 27 35 639 cyclohexane derivatives of the formula I are described

Verbindungen ebenfalls als Aromastoffe von Interesse sind.Compounds are also of interest as flavorings.

Gegenstand der Erfindung sind somit Cyclopentan-Derivate der Formel IIThe invention thus relates to cyclopentane derivatives of the formula II

(III)(III)

in der R1, R2, R3 und R4 nach Anspruch 1 definiert sind, in an sich bekannter Weise in Gegenwart einer Metallcarbonylverbindung als Katalysator hydroformyliert. in which R 1 , R 2 , R 3 and R 4 are defined according to claim 1, hydroformylated in a manner known per se in the presence of a metal carbonyl compound as catalyst.

5. Verwendung der Verbindungen nach Anspruch 1 als Aromastoff für parfümierte Produkte.5. Use of the compounds according to claim 1 as a flavoring for perfumed products.

4545

(D(D

CH-CH2CHOCH-CH 2 CHO

R3 R 3

in der R1 ein Alkylrest, R2 und R3 je ein Wasserstoffatom oder ein Alkylrest, X eine Hydroxylgruppe und Y ein Wasserstoffatom ist oder X und Y zusammen einen Epoxydrest bilden.
Es wurde nun festgestellt, daß gewisse verwandte R1
in which R 1 is an alkyl radical, R 2 and R 3 are each a hydrogen atom or an alkyl radical, X is a hydroxyl group and Y is a hydrogen atom or X and Y together form an epoxy radical.
It has now been found that certain related R 1

1515th

R2 R 2

ΟΗΟΗ

CH-CH2CHOCH-CH 2 CHO

R3 R 3

(H)(H)

in der R1 und R4 je einen Ci-4-Alkylrest und R2 und R3 je ein Wasserstoffatom oder einen Ci _4-Alkylrest bedeuten. in which R 1 and R 4 each denote a Ci-4-alkyl radical and R 2 and R 3 each denote a hydrogen atom or a Ci -4-alkyl radical.

R1, R2 oder R3 sind insbesondere Methylreste. Vor-20 zugsweise ist einer der Reste R2 oder R3 ein Ci _4-Alkylrest und der andere ein Wasserstoffatom.R 1 , R 2 or R 3 are, in particular, methyl radicals. Preferably, one of the radicals R 2 or R 3 is a C 1-4 alkyl radical and the other is a hydrogen atom.

Eine besonders bevorzugte Verbindung der Formel II ist3-(2,3-Dimethyl-3-hydroxycyclopentyl)-butanal.A particularly preferred compound of the formula II is 3- (2,3-dimethyl-3-hydroxycyclopentyl) butanal.

Die Erfindung betrifft ferner ein Verfahren zur Herstellung der Verbindung der Formel II, das dadurch gekennzeichnet ist, daß man ein Olefin der Formel IIIThe invention also relates to a method of production the compound of the formula II, which is characterized in that an olefin of the formula III

3030th

3535

(IH)(IH)

R2 C = CH2 R 2 C = CH 2

in der R1, R2, R3 und R4 wie in bezug auf Formel II definiert sind, in an sich bekannter Weise in Gegenwart einer Metallcarbonylverbindung als Katalysator hydroformyliert. in which R 1 , R 2 , R 3 and R 4 are as defined in relation to formula II, hydroformylated in a manner known per se in the presence of a metal carbonyl compound as catalyst.

Als Katalysator im erfindungsgemäßen Verfahren geeignet ist eine Kobalt- oder Rhodiumcarbonylverbindung; bevorzugt ist ein Rhodiumcarbonylkomplex, insbesondere ein Komplex, der Hydrid- und/oder Phosphingruppen enthält. Der Katalysator kann homogen sein, wie die Verbindung der FormelA cobalt or rhodium carbonyl compound is suitable as a catalyst in the process according to the invention; A rhodium carbonyl complex is preferred, in particular a complex which is hydride and / or Contains phosphine groups. The catalyst can be homogeneous, like the compound of the formula

HRh(CO)[P(C6H5)3],HRh (CO) [P (C6H5) 3],

oder heterogen, z. B. diese Verbindung auf einem festen Träger, wie Kieselgel, enthalten.or heterogeneous, e.g. B. contain this compound on a solid support such as silica gel.

Die erfindungsgemäße Hydroformylierung erfolgt vorzugsweise bei einer Temperatur von 50 bis 2000C und einem Gesamtdruck von Kohlenmonoxid und Wasserstoff bis zu 200 bar. Man kann das erfindungsgemäße Verfahren in einem organischen Lösungsmittel durchführen, z. B. in einem aliphatischen, cycloaliphatischen oder aromatischen Kohlenwasserstoff.The hydroformylation according to the invention is preferably carried out at a temperature of 50 to 200 ° C. and a total pressure of carbon monoxide and hydrogen of up to 200 bar. The inventive method can be carried out in an organic solvent, e.g. B. in an aliphatic, cycloaliphatic or aromatic hydrocarbon.

Die erfindungsgemäßen Verbindungen können in bekannter Weise in der Parfümerie verwendet werden, z. B. als Aromastoff für parfümierte Produkte in Kombination mi' anderen herkömmlichen HilfsStoffen, z. B. für Seifen, Deodorantien, Reinigungsmittel und Aerosole.The compounds according to the invention can be used in a known manner in perfumery, z. B. as a flavoring for perfumed products in combination with other conventional auxiliaries, e.g. B. for Soaps, deodorants, detergents and aerosols.

Die Beispiele erläutern die Erfindung.The examples illustrate the invention.

Die NMR-Spektren in ppm wurden bei 60 MHz in deuteriertem Chloroform gemessen und mit einem Tetramethylsilan-Standard verglichen.The ppm NMR spectra were measured at 60 MHz in deuterated chloroform and with a tetramethylsilane standard compared.

ftft

Beispiel 1example 1

Als Katalysator für die Hydroformylierung wird ein heterogener Katalysator verwendet, der durch Umsetzen von Kieselgel mit einem vorgebildeten Komplex vonThe catalyst used for the hydroformylation is a heterogeneous catalyst which is produced by reacting of silica gel with a preformed complex of

(C2H5O)3SiCH2CH2P(C6Hs)2 mit RhHiCOXPfCeHshli(C 2 H 5 O) 3 SiCH 2 CH 2 P (C 6 Hs) 2 with RhHiCOXPfCeHshli

hergestellt wurde und etwa 1,0 Gewichtsprozent Rhodi- to um enthält.and contains about 1.0 percent by weight rhodium.

Als Ausgangsmaterial wird ein Isomerengemisch von ^-Dimethyl-l-il-methylvinyO-cyclopent-S-ol (Plinol) verwendet, das durch thermisches Kracken von Linalool bei 525° C hergestellt wurde.The starting material is an isomer mixture of ^ -Dimethyl-l-il-methylvinyO-cyclopent-S-ol (Plinol) used, which was made by thermal cracking of linalool at 525 ° C.

8,0 g des Plinolgemisches, 2,0 g des Hydroformylierungskatalysators, 5 ml Benzol und 40 ml Cyclohexan werden in einem 100 ml fassenden Autoklaven aus rostfreiem Stahl vermischt. Der Autoklav wird mit einem Gemisch aus gleichen Volumina Wasserstoff und Koh-Ienmonoxid bis zu einem Druck von 80 bar beaufschlagt. Das Gemisch wird bei 1000C 4 Stunden, 30 Minuten gerührt, dann auf Raumtemperatur abgekühlt, filtriert und fraktioniert destilliert Man erhält 5,3 g 3-(2,3-Dimethyl-3-hydroxycyclopentyl)-butanal, Kp. 100 bis 103° C/120 Pa.8.0 g of the Plinol mixture, 2.0 g of the hydroformylation catalyst, 5 ml of benzene and 40 ml of cyclohexane are mixed in a 100 ml stainless steel autoclave. The autoclave is pressurized with a mixture of equal volumes of hydrogen and carbon monoxide up to a pressure of 80 bar. The mixture is stirred at 100 ° C. for 4 hours, 30 minutes, then cooled to room temperature, filtered and fractionally distilled. 5.3 g of 3- (2,3-dimethyl-3-hydroxycyclopentyl) butanal, boiling point 100 to 103 are obtained ° C / 120 Pa.

Das Produkt hat folgendes NMR-Spektrum (ppm):The product has the following NMR spectrum (ppm):

δ = 0,77(Dublett,3H), δ = 0.77 (doublet, 3H),

0,80(Dublett,3H),0.80 (doublet, 3H),

0,97(Dublett,3H),0.97 (doublet, 3H),

l,30(Singulett,3H),1.30 (singlet, 3H),

9,83 (Multiple«, IH).9.83 (Multiple ", IH).

Das Produkt hat einen ausgeprägten Maiglöckchengeruch. The product has a pronounced lily of the valley odor.

Beispiel 2Example 2

Aus den folgenden Bestandteilen wird ein parfümiertes Produkt mit einem Maiglöckchengeruch hergestellt:A perfumed product with a lily of the valley odor is made from the following ingredients:

4545

5050

5555

6060

*) lOprozentige Lösung in Diäthylen-glykolmonoäthyläther.*) 10 percent solution in diethylene glycol monoethyl ether.

Dieses Präparat hat einen zufriedenstellenden Maiglöckchenähnlichen Geruch. Die Geruchseigenschaften werden jedoch durch Zugabe von 200 Gewichtsteilen Plinolaldehyd sehr stark verbessert und abgerundet.This preparation has a satisfactory lily of the valley-like appearance Odor. However, the odor properties are improved by adding 200 parts by weight Plinolaldehyde very much improved and rounded.

CitronellolCitronellol GewichtsteileParts by weight titi HydroxycitronellalHydroxycitronellal 200200 r,r, LinaloolLinalool 150150 LinalylacetatLinalyl acetate 100100 /?-Phenyläthanol/? - phenylethanol 50 .50 hH Λ-Ιοηοη*Λ-Ιοηοη * 50.50 CitronellylacetatCitronellyl acetate 5050 tt TerpineolTerpineol 3030th f1 f 1 4-(Tricyclo-5.2.1.026-decylid-4- (Tricyclo-5.2.1.0 26 -decylid- 3030th I V
C
1* 1
IV
C.
1 * 1
8-en)-butanal*)8-en) -butanal *)
l BenzylacetatBenzyl acetate 3030th rr 2-Methyl-3(p-tert.-butylphenyl)-2-methyl-3 (p-tert-butylphenyl) - 2020th ff propanalpropanal M- Pentyl-cinnamylaldehyd M -pentyl cinnamyl aldehyde 2020th i,i, Indol*)Indole *) 2020th CinnamylalkoholCinnamyl alcohol 2020th ¥¥ Acetaldehyd-äthyllinalylacetal*)Acetaldehyde ethyl linalylacetal *) 1010 cis-3-Hexenylacetat*)cis-3-hexenyl acetate *) 1010 1010 800800

Claims (4)

Patentansprüche:Patent claims: 1. Cyclopentan-Derivate der Formel II
R1
1. Cyclopentane derivatives of the formula II
R 1
CH-CH2CHOCH-CH 2 CHO in der R1 und R" je einen Ci_4-Alkylrest und R2 und R3 je ein Wasserstoffatom oder einen Ci_4-Alkylrest bedeuten.in which R 1 and R ″ each denote a Ci_4-alkyl radical and R 2 and R 3 each denote a hydrogen atom or a Ci_4-alkyl radical.
2. Cyclopentan-Derivate nach Anspruch 1, dadurch gekennzeichnet, daß einer der Reste R2 oder R3 ein Ci_4-AIkylrest und der andere ein Wasserstoffatom ist.2. Cyclopentane derivatives according to claim 1, characterized in that one of the radicals R 2 or R 3 is a Ci_4-alkyl radical and the other is a hydrogen atom. 3.3-(2,3-Dimethyl-3-hydroxycyclopentyI)-butanal.3.3- (2,3-Dimethyl-3-hydroxycyclopentyI) butanal. 4. Verfahren zur Herstellung der Cyclopentan-Derivate nach Anspruch 1, dadurch gekennzeichnet, daß man ein Olefin der Formel III4. Process for the preparation of the cyclopentane derivatives according to claim 1, characterized in that an olefin of the formula III R1 R 1 OHOH R2 C = CH2 R 2 C = CH 2 R3 R 3
DE19772753644 1976-12-03 1977-12-01 Cyclopentane derivatives, process for their preparation and their use Expired DE2753644C2 (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
GB5050576A GB1550004A (en) 1976-12-03 1976-12-03 Cyclopentane derivatives

Publications (2)

Publication Number Publication Date
DE2753644A1 DE2753644A1 (en) 1978-06-08
DE2753644C2 true DE2753644C2 (en) 1986-09-25

Family

ID=10456151

Family Applications (1)

Application Number Title Priority Date Filing Date
DE19772753644 Expired DE2753644C2 (en) 1976-12-03 1977-12-01 Cyclopentane derivatives, process for their preparation and their use

Country Status (6)

Country Link
JP (1) JPS6031813B2 (en)
CH (1) CH631148A5 (en)
DE (1) DE2753644C2 (en)
FR (1) FR2372784A1 (en)
GB (1) GB1550004A (en)
NL (1) NL7713270A (en)

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2837480A1 (en) * 1978-08-28 1980-03-20 Ruhrchemie Ag METHOD FOR PRODUCING 3- (4-METHYL-3-CYCLOHEXEN-L-YL) BUTYRALDEHYDE
JPH0379714U (en) * 1989-12-08 1991-08-14
JPH0431000U (en) * 1990-07-11 1992-03-12
ES2167829T3 (en) 1997-11-11 2002-05-16 Firmenich & Cie NITRILS AND ALDEHIDS DERIVED FROM 3-ISOPROPENYL-1,2-DIMETHYL-1-CYCLOPENTANOL AND ITS USE IN PERFUMERIA.
CA3026571A1 (en) 2016-06-06 2017-12-14 Brain Brew Ventures 3.0 Llc Method for creating smoked foods and beverages

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
NICHTS-ERMITTELT

Also Published As

Publication number Publication date
NL7713270A (en) 1978-06-06
DE2753644A1 (en) 1978-06-08
GB1550004A (en) 1979-08-08
JPS5371039A (en) 1978-06-24
FR2372784B1 (en) 1981-01-09
JPS6031813B2 (en) 1985-07-24
CH631148A5 (en) 1982-07-30
FR2372784A1 (en) 1978-06-30

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