DE2753644A1 - CYCLOPENTAN DERIVATIVES, THE PROCESS FOR THEIR PRODUCTION AND THEIR USE - Google Patents

CYCLOPENTAN DERIVATIVES, THE PROCESS FOR THEIR PRODUCTION AND THEIR USE

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Publication number
DE2753644A1
DE2753644A1 DE19772753644 DE2753644A DE2753644A1 DE 2753644 A1 DE2753644 A1 DE 2753644A1 DE 19772753644 DE19772753644 DE 19772753644 DE 2753644 A DE2753644 A DE 2753644A DE 2753644 A1 DE2753644 A1 DE 2753644A1
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DE
Germany
Prior art keywords
alkyl radical
catalyst
formula
cyclopentane derivatives
derivatives
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
DE19772753644
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German (de)
Other versions
DE2753644C2 (en
Inventor
Robin Thomas Gray
Aaldert Johannes De 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
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Shell Internationale Research Maatschappij BV
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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

    • 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
    • C11B9/0026—Essential oils; Perfumes compounds containing an alicyclic ring not condensed with another ring
    • C11B9/003—Essential oils; Perfumes compounds containing an alicyclic ring not condensed with another ring the ring containing less than six carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C35/00—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a ring other than a six-membered aromatic ring
    • C07C35/02—Compounds 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
    • C07C35/06—Compounds 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
    • 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
    • C07C45/49—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reaction with carbon monoxide
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C47/00—Compounds having —CHO groups
    • C07C47/02—Saturated compounds having —CHO groups bound to acyclic carbon atoms or to hydrogen
    • C07C47/19—Saturated compounds having —CHO groups bound to acyclic carbon atoms or to hydrogen containing hydroxy groups
    • C07C47/192—Saturated 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

SHELL INTERNATIONALE RESEARCH MAATSCHAPPIJ B.V. Den Haag, NiederlandeSHELL INTERNATIONAL RESEARCH MAATSCHAPPIJ B.V. The Hague, Netherlands

"Cyclopentan-Derivate, Verfahren zu ihrer Herstellung und ihre Verwendung""Cyclopentane derivatives, process for their preparation and their use "

beanspruchte Priorität: 3. Dezember 1976Claimed priority: December 3, 1976

3. Dezember 1976 - Grossbritannien - Nr. 50505/76Dec. 3, 1976 - Great Britain - No. 50505/76

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 its use for perfumed products.

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

809823/0807809823/0807

(D(D

R' CH-CH2CHO R5 R 'CH-CH 2 CHO R 5

1 2 31 2 3

in der R ein AlkyIrest, R und R je ein Wasserstoffatom oder ein Alkylrest, X eine Hydroxylgruppe und Y ein Wasserstoffatom ist oder X und Y zusammen einen Epoxydrest bilden.in which R is an alkyl radical, R and R are each a hydrogen atom or is an alkyl group, X is a hydroxyl group and Y is a hydrogen atom, or X and Y together form an epoxy group.

Es wurde nun festgestellt, dass gewisse verwandte Verbindungen ebenfalls als Aromastoffe von Interesse sind.It has now been found that certain related 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

,1,1

(ID(ID

H2 CH-CH0OHO H 2 CH-CH 0 OHO

4'4 '

-fund a 2 3-found a 2 3

in der R / r je einen Alkylrest und R und R je ein Wasser stoff atom oder einen Alkylrest bedeuten. in which R / r each represent an alkyl radical and R and R each represent a hydrogen atom or an alkyl radical.

12 312 3

R , R oder R sind vorzugsweise Alkylreste mit 1 bis 4 Kohlenstoffatomen, insbesondere Methylreste. Vorzugsweise ist einer der Reste R oder R ein Alkylrest und der andere ein Wasser- R, R or R are preferably alkyl radicals with 1 to 4 carbon atoms, in particular methyl radicals. One of the radicals R or R is preferably an alkyl radical and the other is a water

809823/0807809823/0807

- r- - r-

3tof£ktom' 3tof £ ktom ' 27 5 36 4 A27 5 36 4 A

Eine besonders bevorzugte Verbindung der Formel II ist 3-(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 Verbindungen der Formel II, das dadurch gekennzeichnet ist, dass man ein Olefin der Formel IIIThe invention also relates to a process for the preparation of the compounds of the formula II, which is characterized in that that an olefin of the formula III

(III)(III)

in der R , R , R und R wie in Formel II definiert sind, in Gegenwart einer Metallcarbonylverbindung als Katalysator hydroformyliert. in which R, R, R and R are as defined in formula II, hydroformylated in the presence of a metal carbonyl compound as catalyst.

Als Katalysator im erfindungsgemässen Verfahren geeignet ist eine Kobalt- oder Rhodiumcarbony!verbindung; bevorzugt ist ein Rhodiumcarbonylkomplex, insbesondere ein Komplex, der Hydrid- und/oder Phosphingruppen enthält. Der Katalysator kann homogen sein, wie die Verbindung der Formel HRh(CO)^P(CßH_)__7 oderA cobalt or rhodium carbon compound is suitable as a catalyst in the process according to the invention; A rhodium carbonyl complex is preferred, in particular a complex which contains hydride and / or phosphine groups. The catalyst can be homogeneous , such as the compound of the formula HRh (CO) ^ P (C ß H _) __ 7 or

wiehow

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

Die erfindungsgemässe Hydroformylierung erfolgt vorzugsweise bei einer Temperatur von 50 bis 200 C und einem Gesamtdruck von Kohlenmonoxid un Hasserstoff bis zu 200 bar. Man kann das er- 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 chloride up to 200 bar. You can

809823/0807809823/0807

Q> 27536U Q> 27536U

finduhgsgemässe Verfahren in einem organischen Lösungsmittel durchführen, z.B. in einem aliphatischen, cycloaliphatischen oder aromatischen Kohlenwasserstoff.according to the method in an organic solvent perform, e.g. 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 mit anderen herkömmlichen Hilfsstoffen, z.B. für Seifen, Desodorantien, Reinigungsmittel und Aerosole.The compounds according to the invention can be used in a known manner in perfumery, for example as a flavoring substance for perfumed products in combination with other conventional auxiliaries, for example for soaps, deodorants, cleaning agents 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 NMR spectra in ppm were measured at 60 MHz in deuterated chloroform and compared with a tetramethylsilane standard.

Beispiel 1example 1

Als Katalysator für die Hydroformylierung wird ein Heterogener Katalysator verwendet, der durch Umsetzen von Kieselgel mit einem vorgebildeten Komplex von (CJLO)1SiCH CH P(C,H), mit RhH(CO)/P(C6H5) 73 hergestellt wurde und etwa 1,0 Gewichtsprozent Rhodium enthält.The catalyst used for the hydroformylation is a heterogeneous catalyst which is produced by reacting silica gel with a pre-formed complex of (CJLO) 1 SiCH CH P (C, H), with RhH (CO) / P (C 6 H 5 ) 7 3 and contains about 1.0 weight percent rhodium.

Als Ausgangsmaterial wird ein Isomerengemisch von 2,3-Dimethyl-1-(1-methylvinyl)-cyclopent-3-ol (Plinol) verwendet, das durch thermisches Kracken von Linalool bei 525 C hergestellt wurde.An isomer mixture of 2,3-dimethyl-1- (1-methylvinyl) -cyclopent-3-ol (Plinol), which was produced by thermal cracking of linalool at 525 ° C., is used as the starting material.

80 982 37 0 80 780 982 37 0 80 7

8,0 g* des Plinolgemisches, 2,0g 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 Kohlenmonoxid bis zu einem Druck von 80 bar beaufschlagt. Das Gemisch wird bei 100°C 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 1O3°C/12O 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 in one. 100 ml stainless steel autoclave mixed. The autoclave is filled with a mixture of equal volumes Hydrogen and carbon monoxide pressurized up to 80 bar. The mixture is at 100 ° C for 4 hours, 30 minutes stirred, then cooled to room temperature, filtered and fractionally distilled. 5.3 g of 3- (2,3-dimethyl-3-hydroxycyclopentyl) butanal, boiling point 100 to 10 3 ° C./12O Pa, are obtained.

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

0 =0,77 (publett, 3H), 0,80 (Dublett, 3H) , 0,97 (Dublett, 3H), 1,30 (Singulett, 3H) 9,83 (Multiplett, 1H). 0 = 0.77 (publet, 3H), 0.80 (doublet, 3H), 0.97 (doublet, 3H), 1.30 (singlet, 3H) 9.83 (multiplet, 1H).

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 smell is made from the following ingredients:

809823/0807809823/0807

- sr- - sr-
gG CitronellolCitronellol 2753644
Gewichtsteile 2753644
Parts by weight 2020th HydroxycitronellalHydroxycitronellal 200200 2020th LinaloolLinalool 150150 1010 LinalylacetatLinalyl acetate 100100 10
1010
10 ß-Phenyläthanolß-phenylethanol 5050 <X~ Ionon<X ~ Ionon 5050 CitronellylacetatCitronellyl acetate 5050 TerpineolTerpineol 3030th 4-(Tricyclo-5.2.1.O2'6-decylid-8-en)
butanal4- (Tricyclo-5.2.1.O 2 ' 6 -decylid-8-en)
butanal 3030th BenzylacetatBenzyl acetate 3030th 2020th 2-Methyl-3(p-tert.-butylphenyl)-propanal) 202-methyl-3 (p-tert-butylphenyl) propanal) 20 OZ-Pentyl-cinnainyl aldehydOZ-pentyl-cinnainyl aldehyde Indol+ Indole + CinnamylalkoholCinnamyl alcohol Acetaldehyd-äthyllinalylacetal
cis-3-HexenylacetatAcetaldehyde ethyl linalylacetal
cis -3-hexenyl acetate

800 +'lOprozentige Lösung in Diäthylen-glykolmonoäthylather.800 + 10 percent solution in diethylene glycol monoethyl ether.

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

809823/0807809823/0807

Claims (9)

PatentansprücheClaims 1. Cyclopentan-Derivate der Formel II1. Cyclopentane derivatives of the formula II OHOH B1 B 1 B2 CH-CH9OHO ■■>B 2 CH-CH 9 OHO ■■> i?i? 14 214 2 in der R und R je einen Alkylrest und R und R je ein Wasserstoffatom oder einen Alkylrest bedeuten.in which R and R each represent an alkyl radical and R and R each represent a hydrogen atom or an alkyl radical. 2. Cyclopentan-Derivate nach Anspruch 1, dadurch gekenn-2. Cyclopentane derivatives according to claim 1, characterized 2 zeichnet, dass einer der Reste R oder R ein Alkylrest und der andere ein Wasserstoffatom ist.2 indicates that one of the radicals R or R is an alkyl radical and the other is a hydrogen atom. 3. Cyclopentan-Derivate nach Anspruch 1 und 2, dadurch gekennzeichnet, dass der Alkylrest 1 bis 4 Kohlenstoffatome hat.3. Cyclopentane derivatives according to claim 1 and 2, characterized in that that the alkyl radical has 1 to 4 carbon atoms. 4. 3-(2,S-Dimethyl-S-hydroxycyclopentyl)-butanal.4. 3- (2, S-Dimethyl-S-hydroxycyclopentyl) butanal. 5. Verfahren zur Herstellung der Cyclopentan-Derivate nach Anspruch 1, dadurch gekennzeichnet, dass man ein Olefin der Formel III 5. Process for the preparation of the cyclopentane derivatives according to claim 1, characterized in that an olefin of the formula III 809823/0807809823/0807 Z 27536U Z 27536U (III)(III) 12 3 4
in der R , R , R und R nach Anspruch 1 definiert sind, in Gegenwart einer Metallcarbonylverbindung als Katalysator hydroformyliert.12 3 4
in which R, R, R and R are defined according to claim 1, hydroformylated in the presence of a metal carbonyl compound as catalyst. 6. Verfahren nach Anspruch 5, dadurch gekennzeichnet, dass man als Katalysator einen Rhodiumcarbonyl-Komplex verwendet.6. The method according to claim 5, characterized in that a rhodium carbonyl complex is used as the catalyst. 7. Verfahren nach Anspruch 5 und 6, dadurch gekennzeichnet, dass man einen Rhodiumcarbonyl-Komplex verwendet, der Hydrid- und/oder Phosphingruppen enthält.7. The method according to claim 5 and 6, characterized in that a rhodium carbonyl complex is used which Contains hydride and / or phosphine groups. 8. Verfahren nach Anspruch 5 bis 7, dadurch gekennzeichnet, dass man als Katalysator eine Verbindung der Formel RhH(CO)/P(C6H5)3_73 verwendet.8. The method according to claim 5 to 7, characterized in that a compound of the formula RhH (CO) / P (C 6 H 5 ) 3 _7 3 is used as a catalyst. 9. Verwendung der Verbindungen nach Anspruch 1 bis 4 als Aromastoff für parfümierte Produkte.9. Use of the compounds according to claim 1 to 4 as a flavoring for perfumed products. 809823/080 7809823/080 7
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

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

Family

ID=10456151

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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)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0008459A1 (en) * 1978-08-28 1980-03-05 Ruhrchemie Aktiengesellschaft Process for the production of 3-(4-methyl-3-cyclohexene-1-yl)-butyraldehyde

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0379714U (en) * 1989-12-08 1991-08-14
JPH0431000U (en) * 1990-07-11 1992-03-12
DE69803429T2 (en) 1997-11-11 2002-09-05 Firmenich & Cie Nitriles and aldehydes derived from 3-isopropenyl-1,2-dimethyl-1-cyclopentanol and their use in perfumery

Non-Patent Citations (1)

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

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0008459A1 (en) * 1978-08-28 1980-03-05 Ruhrchemie Aktiengesellschaft Process for the production of 3-(4-methyl-3-cyclohexene-1-yl)-butyraldehyde

Also Published As

Publication number Publication date
GB1550004A (en) 1979-08-08
JPS6031813B2 (en) 1985-07-24
JPS5371039A (en) 1978-06-24
NL7713270A (en) 1978-06-06
FR2372784A1 (en) 1978-06-30
FR2372784B1 (en) 1981-01-09
DE2753644C2 (en) 1986-09-25
CH631148A5 (en) 1982-07-30

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