CH643525A5 - 2-METHYLENE-3- (4-METHYLCYCLOHEX-3-ENYL) -BUTANAL AND 2-METHYLENE-3- (4-METHYLCYCLOHEXYL) -BUTANAL. - Google Patents
2-METHYLENE-3- (4-METHYLCYCLOHEX-3-ENYL) -BUTANAL AND 2-METHYLENE-3- (4-METHYLCYCLOHEXYL) -BUTANAL. Download PDFInfo
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- CH643525A5 CH643525A5 CH388480A CH388480A CH643525A5 CH 643525 A5 CH643525 A5 CH 643525A5 CH 388480 A CH388480 A CH 388480A CH 388480 A CH388480 A CH 388480A CH 643525 A5 CH643525 A5 CH 643525A5
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- Switzerland
- Prior art keywords
- butanal
- methylene
- enyl
- methylcyclohex
- methylcyclohexyl
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- FFFSOJPRLLQQAA-UHFFFAOYSA-N 3-(4-methylcyclohex-3-en-1-yl)-2-methylidenebutanal Chemical compound O=CC(=C)C(C)C1CCC(C)=CC1 FFFSOJPRLLQQAA-UHFFFAOYSA-N 0.000 title claims description 9
- YIAJIVSUDZUUOG-UHFFFAOYSA-N 3-(4-methylcyclohexyl)-2-methylidenebutanal Chemical compound O=CC(=C)C(C)C1CCC(C)CC1 YIAJIVSUDZUUOG-UHFFFAOYSA-N 0.000 title claims description 6
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 35
- VJYFMQREUJXCQV-UHFFFAOYSA-N Limonene aldehyde Chemical compound O=CCC(C)C1CCC(C)=CC1 VJYFMQREUJXCQV-UHFFFAOYSA-N 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 8
- 150000001875 compounds Chemical class 0.000 claims description 7
- 238000002360 preparation method Methods 0.000 claims description 6
- YZFPDESEFZSBIN-UHFFFAOYSA-N 3-(4-methylcyclohexyl)butanal Chemical compound O=CCC(C)C1CCC(C)CC1 YZFPDESEFZSBIN-UHFFFAOYSA-N 0.000 claims description 5
- 238000005984 hydrogenation reaction Methods 0.000 claims description 5
- 230000003197 catalytic effect Effects 0.000 claims description 2
- 125000000467 secondary amino group Chemical class [H]N([*:1])[*:2] 0.000 claims 1
- 150000001299 aldehydes Chemical class 0.000 description 10
- 239000003054 catalyst Substances 0.000 description 9
- JQVDAXLFBXTEQA-UHFFFAOYSA-N dibutylamine Chemical compound CCCCNCCCC JQVDAXLFBXTEQA-UHFFFAOYSA-N 0.000 description 8
- XMGQYMWWDOXHJM-UHFFFAOYSA-N limonene Chemical compound CC(=C)C1CCC(C)=CC1 XMGQYMWWDOXHJM-UHFFFAOYSA-N 0.000 description 5
- 150000003335 secondary amines Chemical class 0.000 description 5
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 4
- -1 Methylene aldehydes Chemical class 0.000 description 3
- 239000012043 crude product Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- YIWUKEYIRIRTPP-UHFFFAOYSA-N 2-ethylhexan-1-ol Chemical compound CCCCC(CC)CO YIWUKEYIRIRTPP-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 229910002091 carbon monoxide Inorganic materials 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 238000004587 chromatography analysis Methods 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 239000008098 formaldehyde solution Substances 0.000 description 2
- 239000003205 fragrance Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 2
- 229940087305 limonene Drugs 0.000 description 2
- 235000001510 limonene Nutrition 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 2
- 229910052703 rhodium Inorganic materials 0.000 description 2
- 239000010948 rhodium Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- ROLMZTIHUMKEAI-UHFFFAOYSA-N 4,5-difluoro-2-hydroxybenzonitrile Chemical compound OC1=CC(F)=C(F)C=C1C#N ROLMZTIHUMKEAI-UHFFFAOYSA-N 0.000 description 1
- ZTQSAGDEMFDKMZ-UHFFFAOYSA-N Butyraldehyde Chemical compound CCCC=O ZTQSAGDEMFDKMZ-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- 238000006683 Mannich reaction Methods 0.000 description 1
- 229930040373 Paraformaldehyde Natural products 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 239000007859 condensation product Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 150000002081 enamines Chemical class 0.000 description 1
- 238000004508 fractional distillation Methods 0.000 description 1
- 238000007037 hydroformylation reaction Methods 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- JXYZHMPRERWTPM-UHFFFAOYSA-N hydron;morpholine;chloride Chemical compound Cl.C1COCCN1 JXYZHMPRERWTPM-UHFFFAOYSA-N 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 1
- QHCCDDQKNUYGNC-UHFFFAOYSA-N n-ethylbutan-1-amine Chemical compound CCCCNCC QHCCDDQKNUYGNC-UHFFFAOYSA-N 0.000 description 1
- AGVKXDPPPSLISR-UHFFFAOYSA-N n-ethylcyclohexanamine Chemical compound CCNC1CCCCC1 AGVKXDPPPSLISR-UHFFFAOYSA-N 0.000 description 1
- GFAQQAUTKWCQHA-UHFFFAOYSA-N n-propylpentan-1-amine Chemical compound CCCCCNCCC GFAQQAUTKWCQHA-UHFFFAOYSA-N 0.000 description 1
- 229920002866 paraformaldehyde Polymers 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- NQRYJNQNLNOLGT-UHFFFAOYSA-N tetrahydropyridine hydrochloride Natural products C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 description 1
Classifications
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- 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
- C11B9/0034—Essential oils; Perfumes compounds containing an alicyclic ring not condensed with another ring the ring containing six carbon atoms
-
- 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
- C07C45/62—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 hydrogenation of carbon-to-carbon double or triple bonds
-
- 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
- C07C45/75—Reactions with formaldehyde
-
- 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
Description
Die vorliegende Erfindung betrifft die zwei Verbindungen 2-Methylen-3-(4-methylcyclohex-3-enyl)-butanal und 2-Me-thylen-3-(4-methylcyclohexyl)-butanal und ein Verfahren zu deren Herstellung. The present invention relates to the two compounds 2-methylene-3- (4-methylcyclohex-3-enyl) butanal and 2-methylene-3- (4-methylcyclohexyl) butanal and a process for their preparation.
Die Herstellung von Methylenaldehyden kann auf verschiedenen Wegen erfolgen. Nach der Mannich-Reaktion setzt man Ammoniak oder ein primäres bzw. sekundäres Amin, das gewöhnlich als Salz z.B. als Hydrochlorid vorliegt, mit Formaldehyd und einer Verbindung, die ein reaktionsfähiges Wasserstoffatom enthält, um. Nach einem in der US-PS 2 518 416 beschriebenen Verfahren leitet man das Gemisch aus Aldehyd, dessen a-Stellung zur Carbonyl-gruppe eine CH2-Gruppe besitzt, und Formaldehyd durch die Schmelze eines Salzes aus einem primären oder sekundären Amin und einer starken Säure. Ferner hat man zur , Kondensation von aliphatischen Aldehyden mit Formaldehyd auch Piperidin-Hydrochlorid, Morpholin-Hydro-chlorid oder ein Ammoniumsalz, wie Ammoniumchlorid, eingesetzt (vgl. US-PS 2 639 295). Methylene aldehydes can be prepared in various ways. After the Mannich reaction, ammonia or a primary or secondary amine, usually used as a salt e.g. is in the form of hydrochloride, with formaldehyde and a compound containing a reactive hydrogen atom. According to a process described in US Pat. No. 2,518,416, the mixture of aldehyde, the a-position of which has a CH2 group to the carbonyl group, and formaldehyde is passed through the melt of a salt of a primary or secondary amine and a strong acid . Furthermore, piperidine hydrochloride, morpholine hydrochloride or an ammonium salt such as ammonium chloride have also been used for the condensation of aliphatic aldehydes with formaldehyde (cf. US Pat. No. 2,639,295).
Ein neues, in der DE-Patentanmeldung P 2 855 505.7 beschriebenes Verfahren führt die Umsetzung von Aldehyden mit Formaldehyd zur Herstellung von 2-Methylenal-dehyden in Gegënwart katalytischer Mengen eines Enamins durch. Diese Arbeitsweise erweist sich gegenüber dem bekannten Verfahren als wirtschaftlich vorteilhaft und technisch leicht durchführbar. A new process, described in DE patent application P 2 855 505.7, carries out the reaction of aldehydes with formaldehyde to produce 2-methylenealdehydes in the presence of catalytic amounts of an enamine. This method of operation proves to be economically advantageous and technically easy to carry out compared to the known method.
Durch Hydroformylierung kann Limonen (l-Methyl-4-isopropenyl-cyclohex-l-en) leicht in 3-(4-Methylcyclohex-3-enyl)-butanal überführt werden. Die Hydroformulierung, d.h. die Umsetzung der olefinisch ungesättigten Verbindung mit Kohlenmonoxid und Wasserstoff, kann nach verschiedenen Verfahren erfolgen, die sich im wesentlichen durch die Art des verwendeten Katalysators unterscheiden. So ist es bekannt, als Katalysator Kobaltcarbonylverbindungen, die neben Kohlenmonoxid zusätzlich Trialkyl- bzw. Triaryl-phosphine als Liganden enthalten, zu verwenden oder in Gegenwart von Rhodiumcarbonylkomplexen zu arbeiten. Besonders bewährt hat es sich, Rhodiumcarbònyle einzusetzen, die zusätzlich Triphenyl- oder Trialkylphosphine enthalten, Drücke von 100 bis 350 bar und Temperaturen von 110 bis 160°C anzuwenden. (Vgl. DE-Patentanmeldung P 2 837 480). Limonene (1-methyl-4-isopropenyl-cyclohex-1-ene) can easily be converted to 3- (4-methylcyclohex-3-enyl) butanal by hydroformylation. The hydroformulation, i.e. the reaction of the olefinically unsaturated compound with carbon monoxide and hydrogen can be carried out by various processes which differ essentially in the type of catalyst used. Thus, it is known to use cobalt carbonyl compounds as catalysts, which contain trialkyl or triarylphosphines as ligands in addition to carbon monoxide, or to work in the presence of rhodium carbonyl complexes. It has proven particularly useful to use rhodium carbonyls which additionally contain triphenyl- or trialkylphosphines, to use pressures from 100 to 350 bar and temperatures from 110 to 160.degree. (See DE patent application P 2 837 480).
Ausgehend von 3-(4-Methylcyclohex-3-enyl)-butanal erhält man durch Methylenierung mit Formaldehyd 2-Me-thylen-3-(4-methylcyclohex-3-enyl)-butanal. Wird das Produkt der partiellen Hydrierung von 3-(4-Methylcyclohex-3-enyl)-butanal nämlich 3-(4-Methylcyclohexyl)-butanal mit Formaldehyd umgesetzt, gelangt man zum 2-Methylen-3-(4-methylcyclohexyl)-butanal. Starting from 3- (4-methylcyclohex-3-enyl) butanal, methyleneation with formaldehyde gives 2-methylene-3- (4-methylcyclohex-3-enyl) butanal. If the product of the partial hydrogenation of 3- (4-methylcyclohex-3-enyl) butanal, namely 3- (4-methylcyclohexyl) butanal, is reacted with formaldehyde, 2-methylene-3- (4-methylcyclohexyl) butanal is obtained .
Die Herstellung der beiden neuen Verbindungen erfolgt nach dem im Patentanspruch 2 definierten Verfahren. Als sekundäres Amin wird vorteilhaft Di-n-butylamin eingesetzt. Man erhält auf diesem Wege unmittelbar 2-Methylen-3-(4-methylcyclohex-3-enyl)-butanal. 2-Methylen-3-(4-methylcy-clohexyl)-butanal ist auf dem gleichen Weg, jedoch nach vorhergehender partieller Hydrierung des Ausgangsaldehyds zugänglich. The two new connections are produced by the method defined in claim 2. Di-n-butylamine is advantageously used as the secondary amine. In this way, 2-methylene-3- (4-methylcyclohex-3-enyl) butanal is obtained directly. 2-methylene-3- (4-methylcy-clohexyl) butanal can be obtained in the same way, but after partial hydrogenation of the starting aldehyde.
Zur Herstellung von 2-Methylen-3-(4-methylcyclohex-3-enyl)-butanal werden 3-(4-Methylcyclohex-3-enyl)-butanal und Formaldehyd zweckmässig im Molverhältnis 1:1 eingesetzt. Ein geringer Überschuss einer der beiden Komponenten schadet nicht, ist jedoch entbehrlich. Der Formaldehyd kann als reine Verbindung verwendet werden, oder aber als Lösung in einem Lösungsmittel, z.B. Wasser. Statt von Formaldehyd kann man auch von Verbindungen ausgehen, die unter bestimmten Bedingungen Formaldehyd bilden, z.B. den Kondensationsprodukten des Formaldehyds, wie Paraformaldehyd. For the preparation of 2-methylene-3- (4-methylcyclohex-3-enyl) butanal, 3- (4-methylcyclohex-3-enyl) butanal and formaldehyde are expediently used in a molar ratio of 1: 1. A small excess of one of the two components does no harm, but is unnecessary. The formaldehyde can be used as a pure compound or as a solution in a solvent, e.g. Water. Instead of formaldehyde, it is also possible to start from compounds which formaldehyde under certain conditions, e.g. the condensation products of formaldehyde, such as paraformaldehyde.
Als Katalysator verwendet man sekundäre Amine, die gleiche oder verschiedene Alkylreste enthalten können. Beispiele sind N-Ethyl-n-butylamin, N-Propyl-n-pentylamin oder N-Ethyl-cyclohexylamin. Besonders bewährt hat sich Di-n-butylamin. Bezogen auf ein Mol Formaldehyd verwendet man beispielsweise 0,01 bis 0,05 Mol sekundäres Amin, vorzugsweise 0,025 Mol. Die Reaktion wird bei Temperaturen von 60 bis 120°C und insbesondere bei 80 bis 100°C vorgenommen. Secondary amines, which may contain the same or different alkyl radicals, are used as the catalyst. Examples are N-ethyl-n-butylamine, N-propyl-n-pentylamine or N-ethyl-cyclohexylamine. Di-n-butylamine has proven particularly useful. Based on one mole of formaldehyde, for example 0.01 to 0.05 mol of secondary amine, preferably 0.025 mol, is used. The reaction is carried out at temperatures from 60 to 120 ° C. and in particular at 80 to 100 ° C.
Zur Durchführung der Methylenierung setzt man 3-(4-Methylcyclohex-3-enyl)-butanal lin Gegenwart des Katalysators mit Formaldehyd oder der Formaldehyd liefernden Substanz unmittelbar um. Die Anwesenheit eines Lösungsmittels wie Wasser oder Alkohol (z.B. Isobutanol oder 2-Ethylhe-xanol) ist zweckmässig. To carry out the methyleneation, 3- (4-methylcyclohex-3-enyl) -butanal is reacted directly with formaldehyde or the substance providing formaldehyde in the presence of the catalyst. The presence of a solvent such as water or alcohol (e.g. isobutanol or 2-ethylhexanol) is advisable.
Die Isolierung des Reaktionsproduktes kann durch fraktionierte Destillation erfolgen. Die Verbindung wird dann in einer Form erhalten, die ihren unmittelbaren Einsatz als Endprodukt erlaubt. The reaction product can be isolated by fractional distillation. The compound is then obtained in a form that allows it to be used directly as an end product.
Durch partielle Hydrierung von 3-(4-Methylcyclohex-3-enyl)-butanal gelangt man zu 3-(4-Methylcyclohexyl)-butanal. Üblicherweise erfolgt die Umsetzung mit Wasserstoffin einem Druckgefäss in Gegenwart von Katalysatoren. Je nach Art des Katalysators kann man einen Druck von 1 bis 150 bar anwenden und eine Temperatur von 20 bis 120°C einhalten. Als Hydrierkatalysatoren kommen Edelmetalle, z.B. Palladium und Platin in Betracht. Besonders bewährt haben sich Palladium-Katalysatoren. Zweckmässig wendet man den Katalysator in Konzentrationen von 0,5 bis 2 Gew.-%, bezogen auf den eingesetzten Aldehyd, an. Die Hydrierung kann unter Zusatz eines Lösungsmittels erfolgen, doch ist dies nicht unbedingt erforderlich. Zur Reingewinnung des 3-(4-Methylcyclohexyl)-butanals wird das Rohprodukt nach Abtrennung des Katalysators zweckmässig destilliert. Partial hydrogenation of 3- (4-methylcyclohex-3-enyl) butanal gives 3- (4-methylcyclohexyl) butanal. The reaction with hydrogen is usually carried out in a pressure vessel in the presence of catalysts. Depending on the type of catalyst, a pressure of 1 to 150 bar can be used and a temperature of 20 to 120 ° C maintained. Precious metals, e.g. Palladium and platinum are considered. Palladium catalysts have proven particularly useful. The catalyst is expediently used in concentrations of 0.5 to 2% by weight, based on the aldehyde used. The hydrogenation can be carried out with the addition of a solvent, but this is not absolutely necessary. In order to obtain the 3- (4-methylcyclohexyl) butanal in pure form, the crude product is expediently distilled after the catalyst has been separated off.
Die Herstellung und Isolierung von 2-Methylen-3-(4-me-thylcyclohexyl)-butanal verläuft in Analogie zum oben beschriebenen 2-Methylen-3-(4-methylcyclohex-3-enyl)-butanal. The preparation and isolation of 2-methylene-3- (4-methylcyclohexyl) butanal is analogous to the 2-methylene-3- (4-methylcyclohex-3-enyl) butanal described above.
Die neuen a-Methylenaldehyde haben besondere Bedeutung als Duftstoffe und weisen Geruchsnuancen auf, durch die sie sich von anderen, auf dem Markt befindlichen Duftstoffen charakteristisch unterscheiden. Ein besonderer Vorteil der neuen Aldehyde ist, dass sie auf Basis eines billigen, in grossen Mengen zur Verfügung stehenden Ausgangsmaterials, dem Limonen, hergestellt werden können. The new a-methylene aldehydes are particularly important as fragrances and have odor nuances that distinguish them from other fragrances on the market. A particular advantage of the new aldehydes is that they can be produced on the basis of an inexpensive starting material, the limonene, which is available in large quantities.
In den nachstehenden Beispielen sind die erfindungsge-mässen Aldehyde näher beschrieben. Die prozentualen Konzentrationsangaben sind gewichtsmässig. The aldehydes according to the invention are described in more detail in the examples below. The percentages of concentration are by weight.
2 2nd
5 5
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IS IS
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Beispiel 1 example 1
Darstellung von 2-Methylen-3-(4-methylcyclohex-3-enyl)-butanal. Preparation of 2-methylene-3- (4-methylcyclohex-3-enyl) butanal.
Eine Mischung von 332 g 3-(4-Methylcyclohex-3-enyl)-butanal, 210g 30%iger wässriger Formaldehydlösung und 13 g Di-n-butylamin wird in einem Kolben 60 Minuten lang, unter Rühren und Rückflusskühlung auf maximal 70°C erhitzt. Nach Abtrennung der Wasserphase isoliert man ein Rohprodukt, das nach gaschromatographischer Analyse neben etwa 1% Ausgangsaldehyd 94% 2-Methylen-Verbindung enthält. Durch Destillation werden 311g eines A mixture of 332 g of 3- (4-methylcyclohex-3-enyl) butanal, 210 g of 30% aqueous formaldehyde solution and 13 g of di-n-butylamine is placed in a flask for 60 minutes, with stirring and reflux cooling to a maximum of 70 ° C heated. After the water phase has been separated off, a crude product is isolated which, according to gas chromatographic analysis, contains 94% 2-methylene compound in addition to about 1% starting aldehyde. By distillation, 311 g of one
3 643525 3 643525
99,4%igen Reinaïdehyds isoliert (Kp: 112°C/Ì3 mbar). Beispiel 2 99.4% pure aldehyde isolated (bp: 112 ° C / Ì3 mbar). Example 2
Darstellung von 2-Methylen-3-(4-methyicyclohexyl)-5 butanal. Preparation of 2-methylene-3- (4-methyicyclohexyl) -5 butanal.
Eine Mischung von 336 g 3-(4-MethyIcyclohexyl)-butanal, 210 g 30%iger wässriger Formaldehydlösung und 13 g Di-n-butylamin wird unter den Bedingungen des Beispiels 1 umgesetzt. Nach gaschromatographischer Analyse enthält das io Rohprodukt neben 1% Ausgangsaldehyd 95% 2-Methylen-Verbindung. Durch Destillation werden 320 g eines 99,l%igen Reinaldehyds isoliert (Kp: 110°C/13 mbar). A mixture of 336 g of 3- (4-methylcyclohexyl) butanal, 210 g of 30% aqueous formaldehyde solution and 13 g of di-n-butylamine is reacted under the conditions of Example 1. According to gas chromatographic analysis, the io crude product contains 1% starting aldehyde and 95% 2-methylene compound. 320 g of a 99.1% pure aldehyde are isolated by distillation (bp: 110 ° C./13 mbar).
B B
Claims (3)
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE2921619A DE2921619C3 (en) | 1979-05-28 | 1979-05-28 | 2-methylene-3- (4-methylcyclohex-3-enyl) butanal and 2-methylene-3- (4-methylcyclohexyl) butanal and processes for their preparation |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CH643525A5 true CH643525A5 (en) | 1984-06-15 |
Family
ID=6071862
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CH388480A CH643525A5 (en) | 1979-05-28 | 1980-05-19 | 2-METHYLENE-3- (4-METHYLCYCLOHEX-3-ENYL) -BUTANAL AND 2-METHYLENE-3- (4-METHYLCYCLOHEXYL) -BUTANAL. |
Country Status (7)
| Country | Link |
|---|---|
| JP (1) | JPS5846509B2 (en) |
| CH (1) | CH643525A5 (en) |
| DE (1) | DE2921619C3 (en) |
| FR (1) | FR2457850A1 (en) |
| GB (1) | GB2054557B (en) |
| IT (1) | IT1147084B (en) |
| SE (1) | SE8003798L (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5021184A (en) * | 1988-10-21 | 1991-06-04 | International Flavors & Fragrances Inc. | Adamantane derivatives, compositions of matter containing same, processes for preparing said adamantane derivatives and said compositions, and organoleptic and deodorancy uses of said adamantane derivatives and said compositions |
| US4956481A (en) * | 1988-10-21 | 1990-09-11 | International Flavors & Fragrances Inc. | Adamantane derivatives, compositions of matter containing same, processes for preparing said adamantane derivatives and said compositions, and organoleptic and deodorancy uses of said adamantane derivatives and said compositions |
| DE19820657A1 (en) * | 1998-05-08 | 1999-11-11 | Henkel Kgaa | Aroma composition cosmetics, technical products or alcoholic perfumery |
| DE10205835B4 (en) * | 2002-02-13 | 2004-11-11 | Celanese Chemicals Europe Gmbh | Process for the preparation of terpinolenaldehyde |
| GB2529901A (en) * | 2014-09-08 | 2016-03-09 | Givaudan Sa | Organic compounds |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2519327A (en) * | 1947-01-13 | 1950-08-15 | Fmc Corp | Condensation of beta-(4-methyl-delta3-cyclohexenyl)-butyraldehyde with aldehydes andketones |
| US2639295A (en) * | 1948-07-16 | 1953-05-19 | Eastman Kodak Co | Manufacture of unsaturated aldehydes |
| US3676505A (en) * | 1969-12-29 | 1972-07-11 | Procter & Gamble | 4-(4-methylcyclohex-3-en-1-yl)pent-4-en-1-ol and a process for its synthesis |
-
1979
- 1979-05-28 DE DE2921619A patent/DE2921619C3/en not_active Expired
-
1980
- 1980-05-14 GB GB8015991A patent/GB2054557B/en not_active Expired
- 1980-05-19 CH CH388480A patent/CH643525A5/en not_active IP Right Cessation
- 1980-05-20 FR FR8011260A patent/FR2457850A1/en not_active Withdrawn
- 1980-05-21 SE SE8003798A patent/SE8003798L/en not_active Application Discontinuation
- 1980-05-27 IT IT48810/80A patent/IT1147084B/en active
- 1980-05-28 JP JP55070231A patent/JPS5846509B2/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| DE2921619C3 (en) | 1982-05-19 |
| IT8048810A0 (en) | 1980-05-27 |
| FR2457850A1 (en) | 1980-12-26 |
| GB2054557A (en) | 1981-02-18 |
| DE2921619B2 (en) | 1981-05-07 |
| JPS55157563A (en) | 1980-12-08 |
| SE8003798L (en) | 1980-11-29 |
| IT1147084B (en) | 1986-11-19 |
| DE2921619A1 (en) | 1980-12-04 |
| GB2054557B (en) | 1983-03-16 |
| JPS5846509B2 (en) | 1983-10-17 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PL | Patent ceased |